Hydrogen Bond in Water molecule

Water Hydrogen Bonding Hydrogen bonding occurs when an atom of hydrogen is attracted by rather strong forces to two atoms instead of only one, so that it may be considered to be acting as a bond between them [99].h Typically this occurs where the partially positively charged hydrogen atom lies between partially negatively charged oxygen and nitrogen atoms, but is also found elsewhere, such as between fluorine atoms in HF2- and between water and the smaller halide ions F-, Cl- and Br- (for example, HO-H····Br-, [178, 1190]; the strength of hydrogen bonding reducing as the halide radius increases), and to a much smaller extent to I- [190] and even xenon [941]. Even very weak C-H····OH2 hydrogen bonds (~ 4 kJ mol-1) are being increasingly recognized [1293]. In theoretical studies, strong hydrogen bonds even occur to the hydrogen atoms in metal hydrides (for example, LiH····HF; [217]). Hydrogen bond strength In water the hydrogen atom is covalently attached to the oxygen of a water molecule (492.2148 kJ mol-1 [350]) but has (optimally) an additional attraction (about 23.3 kJ mol-1a1 [168]; almost 5 x the average thermal collision fluctuation at 25°C)a2 to a neighboring oxygen atom of another water molecule that is far greater than any included van der Waals interactioni. Water's hydrogen bonding holds water molecules up to about 15% closer than if than if water was a simple liquid with just van der Waals interactions. However, as hydrogen bonding is directional it restricts the number of neighboring water molecules to about four rather than the larger number found in simple liquids (for example, xenon atoms have twelve nearest neighbors in the liquid state. Formation of hydrogen bonds between water molecules gives rise to large, but mostly compensating, energetic changes in enthalpy (becoming more negative) and entropy (becoming less positive). Both changes are particularly large, based by per-mass or per-volume basis, due to the small size of the water molecule. This enthalpy-entropy compensation is almost complete, however, with the consequence that very small imposed enthalpic or entropic effects may exert a considerable influence on aqueous systems. It is possible that hydrogen bonds between para-H2O, possessing no ground state spin, are stronger and last longer than hydrogen bonds between orth-H2O [1150]. The hydrogen bond in water is part (about 90%) electrostatic and part (about 10%) covalent [96]d and may be approximated by bonds made up of covalent HO-H····OH2, ionic HOδ--Hδ+····Oδ-H2, and long-bonded covalent HO-··H––O+H2 parts with HO-H····OH2 being very much more in evidence than HO-··H––O+H2, where there would be expected to be much extra non-bonded repulsion. Hydrogen bonding effects all the molecular orbitals even including the inner O1s (1a1) orbital which is bound 318 kJ mol-1 (3.3 eV) less strongly in a tetrahedrally hydrogen bonded bulk liquid phase compared to the gas phase [1227]. X-ray spectroscopic probing indicates that the electron transitions between molecular orbitals (changing with the local hydrogen bonding topology) with differing such contributions may shift on a time scale of less than a femtosecond. Contributing to the strength of water's hydrogen bonding are nuclear quantum effects (zero point vibrational energy) which bias the length of the O-H covalent bond longer than its 'equilibrium' position length (as the shorter HO-H····OH2 hydrogen bonds are stronger), so also increasing the average dipole moment [554]. On forming the hydrogen bond, the donor hydrogen atom stretches away from its oxygen atom and the acceptor lone-pair stretches away from its oxygen atom and towards the donor hydrogen atom [585], both oxygen atoms being pulled towards each other. An important feature of the hydrogen bond is that it possesses direction; by convention this direction is that of the shorter O-H ( " type="#_x0000_t75">) covalent bond (the O-H hydrogen atom being donated to the O-atom acceptor atom on another H2O molecule). In 1H-NMR studies, the chemical shift of the proton involved in the hydrogen bond moves about 0.01 ppm K-1 upfield to lower frequency (plus about 5.5 ppm further upfield to vapor at 100°C); that is, becomes more shielded with reducing strength of hydrogen bonding [222] as the temperature is raised; a similar effect may be seen in water's 17O NMR, moving about 0.05 ppm K-1 upfield plus 36-38 ppm further upfield to vapor at 100°C.b Increased extent of hydrogen bonding within clusters results in a similar effect; that is, higher NMR chemical shifts with greater cooperativity [436]. The bond strength depends on its length and angle, with the strongest hydrogen bonding in water existing in the short linear proton-centered H5O2+ ion at about 120 kJ mol-1. However, small deviations from linearity in the bond angle (up to 20°) possibly have a relatively minor effect [100]. The dependency on bond length is very important and has been shown to exponentially decay with distance [101]. Some researchers consider the hydrogen bond to be brokenc if the bond length is greater than 3.10 Å or the bond angle less than 146° [173],c2 although ab initio calculations indicate that most of the bonding energy still remains and more bent but shorter bonds may be relatively strong; for example, one of the hydrogen bonds in ice-four (143°). Similarly O····H-O interaction energies below 10 kJ mol-1 have been taken as indicative of broken hydrogen bonds although they are almost 50% as strong as 'perfect' hydrogen bonds and there is no reason to presuppose that it is solely the hydrogen bond that has been affected with no contributions from other interactions. Also, the strength of bonding must depend on the orientation and positions of the other bonded and non-bonded atoms and 'lone pair' electrons [525]. There is a trade-off between the covalent and hydrogen bond strengths; the stronger is the H····O bond, the weaker the O-H covalent bond, and the shorter the O····O distance. The weakening of the O-H covalent bond gives rise to a good indicator of hydrogen bonding energy; the fractional increase in its length determined by the increasing strength of the hydrogen bonding [217]; for example, when the pressure is substantially increased (~ GPa) the remaining hydrogen bonds (H····O) are forced shorter [655] causing the O-H covalent bonds to be elongated. Hydrogen bond strength can be affected by electromagnetic and magnetic effects. Dissociation is a rare event, occurring only twice a day that is, only once for every 1016 times the hydrogen bond breaks. Hydrogen bond cooperativity When a hydrogen bond forms between two water molecules, the redistribution of electrons changes the ability for further hydrogen bonding. The water molecule donating the hydrogen atom has increased electron density in its 'lone pair' region [577], which encourages hydrogen bond acceptance, and the accepting water molecule has reduced electron density centered on its hydrogen atoms and its remaining 'lone pair' region [577], which encourages further donation but discourages further acceptance of hydrogen bonds. This electron redistribution thus results in both the cooperativity (e.g. accepting one hydrogen bond encourages the donation of another) and anticooperativity (for example, accepting one hydrogen bond discourages acceptance of another) in hydrogen bond formation in water networks. Cooperative hydrogen bonding increases the O-H bond length whilst causing a 20-fold greater reduction in the H····O and O····O distances [436]. The increase in bond length has been correlated with the hydrogen bond strength and resultant O-H stretch vibrations [1318]. Thus O····O distances within clusters are likely to be shorter than those at the periphery, in agreement with the icosahedral cluster model. If the hydrogen bond is substantially bent then it follows that the bond strength is weaker. The main criteria to determine the strength of hydrogen bonds are their (relatively inaccurately determined) intermolecular distances and the (more precise) wavenumbers of their stretching vibrational modes and those of the donor hydrogen covalent bond.e Any factors, such as polarization, that reduces the hydrogen bond length, is expected to increase its covalency. There is still some dispute over the size of this covalency,d however any covalency will increase the network stability relative to purely electrostatic effects. The hydrogen bond in water dimers is sufficiently strong to result in the dimers persisting within the gas state at significant concentrations (for example, ~0.1% H2O at 25°C and 85% humidity) to contribute significantly to the absorption of sunlight and atmospheric reaction kinetics [266]. The molecular orbitals involved in the hydrogen bonding between two water molecules (50 KB) and five water molecules (29 KB) in a cyclic pentamer are given on other pages. Although the hydrogen atoms are often shown along lines connecting the oxygen atoms, this is now thought to be indicative of time-averaged direction only and unlikely to be found to a significant extent even in ice. Liquid water consists of a mixture of short, straight and strong hydrogen bonds and long, weak and bent hydrogen bonds with many intermediate between these extremes. Short hydrogen bonds in water are strongly correlated with them being straighter [1083]. Proton magnetic shielding studies give the following average parameters for the instantaneous structure of liquid water at 4°C; non-linearity, distances and variance; all increasing with temperature [458]. Note that the two water molecules below are not restricted to perpendicular planes and only a small proportion of hydrogen bonds are likely to have this averaged structure. The hydrogen bond length of water varies with temperature and pressure. As the covalent bond lengths vary much less with temperature and pressure, most of the densification of ice 1h due to reduced temperature or increased pressure must be due to reduction in the hydrogen bond length. This hydrogen bond length variation can be shown from the changes in volume of ice 1h [818]. As hydrogen bond strength depends almost linearly on its length (shorter length giving stronger hydrogen bonding), it also depends almost linearly (outside extreme values) on the temperature and pressure [818]. The latest molecular parameters for water are given elsewhere. At 0 K the O····O distance in ice Ih is 2.75 Å. The energy of a linear hydrogen bond depends on the orientation of the water molecules relative to the hydrogen bond.j Note that in liquid water, the instantaneous hydrogen bonded arrangement of most molecules is not as symmetrical as shown here. In particular, the positioning of the water molecules donating hydrogen bonds to the accepting positions on a water molecule (that is, the water molecules behind in the diagram above, labeled 'd') are likely to be less tetrahedrally placed, due to the lack of substantial tetrahedrally positioned 'lone pair' electrons, than those water molecules that are being donated to from that water molecule (that is, the water molecules top and front in the diagram above, labeled 'a' [1224]. Also, the arrangement may well consist of one pair of more tetrahedrally arranged strong hydrogen bonds (one donor and one acceptor) with the remaining hydrogen bond pair (one donor and one acceptor) being either about 6 kJ mol-1 weaker [573], less tetrahedrally arranged [373, 396] or bifurcated [573]; perhaps mainly due to the anticooperativity effects mentioned below. Such a division of water into higher (4-linked) and lower (2-linked) hydrogen bond coordinated water has been shown by modelling [1349]. X-ray absorption spectroscopy confirms that, at room temperature, 80% of the molecules of liquid water have one (cooperatively strengthened) strong hydrogen bonded O-H group and one non-, or only weakly, bonded O-H group at any instant (sub-femtosecond averaged and such as may occur in pentagonally hydrogen bonded clusters), the remaining 20% of the molecules being made up of four-hydrogen-bonded tetrahedrally coordinated clusters [613]. There is much debate as to whether such structuring represents the more time-averaged structure, which is understood by some to be basically tetrahedral [1024]. g Liquid water contains by far the densest hydrogen bonding of any solvent with almost as many hydrogen bonds as there are covalent bonds. These hydrogen bonds can rapidly rearrange in response to changing conditions and environments (for example, solutes). The hydrogen bonding patterns are random in water (and ice Ih); for any water molecule chosen at random, there is equal probability (50%) that the four hydrogen bonds (that is, the two hydrogen donors and the two hydrogen acceptors) are located at any of the four sites around the oxygen. Water molecules surrounded by four hydrogen bonds tend to clump together, forming clusters, for both statistical [11] and energetic reasons. Hydrogen bonded chains (that is, O-H····O-H····O) are cooperative [379]; the breakage of the first bond is the hardest, then the next one is weakened, and so on (see the cyclic water pentamer). Thus unzipping may occur with complex macromolecules held together by hydrogen bonding, for example, nucleic acids. Such cooperativity is a fundamental property of liquid water where hydrogen bonds are up to 250% stronger than the single hydrogen bond in the dimer [77]. A strong base at the end of a chain may strengthen the bonding further. The cooperative nature of the hydrogen bond means that acting as an acceptor strengthens the water molecule acting as a donor [76]. However, there is an anticooperative aspect in so far as acting as a donor weakens the capability to act as another donor, for example, O····H-O-H····O [77]. It is clear therefore that a water molecule with two hydrogen bonds where it acts as both donor and acceptor is somewhat stabilized relative to one where it is either the donor or acceptor of two. This is the reason why it is suspected that the first two hydrogen bonds (donor and acceptor) give rise to the strongest hydrogen bonds [79]. An interesting way of describing the cooperative/anticooperative nature of the water dimer hydrogen bond is to use the nomenclature d'a'DAd''a'' where DA represents the donor-acceptor nature of the hydrogen bond, the d'a' represents the remaining donor-acceptor status of the donating water molecule and d''a'' represents the remaining donor-acceptor status of the accepting water molecule [852]. Individually, the most energetically favored donating water molecules have the structures 02D, 12D, 01D and 11D with 00D and 10D disfavored whereas the most energetically favored accepting water molecules have the structures A20, A21, A10 and A11 with A00 and A01 disfavored. Cations may induce strong cooperative hydrogen-bonding around them due to the polarization of water O-H by cation-lone pair interactions (Cation+····O-H····O-H). Luck et al [78] introduced a cooperativity factor for this effect, which varied as the Hofmeister series from K+ (1.08) to Zn2+ (2.5). Total hydrogen bonding around ions may be disrupted however as if the electron pair acceptance increases (for example, in water around cations) so the electron pair donating power of these water molecules is reduced; with opposite effects in the hydration water around anions. These changes in the relative hydration ability of salt solutions are responsible for the swelling and deswelling behavior of hydrophilic polymer gels [317]. The substantial cooperative strengthening of hydrogen bond in water is dependent on long range interactions [98]. Breaking one bond generally weakensf those around whereas making one bond generally strengthens those around and this, therefore, encourages larger clusters, for the same average bond density. The hydrogen-bonded cluster size in water at 0°C has been estimated to be 400 [77]. Weakly hydrogen-bonding surface restricts the hydrogen-bonding potential of adjacent water so that these make fewer and weaker hydrogen bonds. As hydrogen bonds strengthen each other in a cooperative manner, such weak bonding also persists over several layers and may cause locally changed solvation. Conversely, strong hydrogen bonding will be evident at distance. The weakening of hydrogen bonds, from about 23 kJ mol-1 to about 17 kJ mol-1, is observed when many bonds are broken at superheating temperatures (> 100°C) so reducing the cooperativity [173]. The breakage of these bonds is not only due to the more energetic conditions at high temperature but also results from a related reduction in the hydrogen bond donating ability by about 10% for each 100°C increase [218]. The loss of these hydrogen bonds results in a small increase in the hydrogen bond accepting ability of water, due possibly to increased accessibility [218]. Every hydrogen bond formed increases the hydrogen bond status of two water molecules and every hydrogen bond broken reduces the hydrogen bond status of two water molecules. The network is essentially complete at ambient temperatures; that is, (almost) all molecules are linked by at least one unbroken hydrogen bonded pathway. Hydrogen bond lifetimes are 1 - 20 ps [255] whereas broken bond lifetimes are about 0.1 ps with the proportion of 'dangling' hydrogen bonds persisting for longer than a picosecond being insignificant [849]. Broken bonds are basically unstable [849] and will probably reform to give same hydrogen bond (as shown by the slow ortho-water/para-water equilibrium process [410]), particularly if the other three hydrogen bonds are in place; hydrogen bond breakage being more dependent on the local structuring rather than the instantaneous hydrogen bond strength [833]. If not, breakage usually leads to rotation around one of the remaining hydrogen bond(s) [673] and not to translation away, as the resultant 'free' hydroxyl group and 'lone pair' are both quite reactive. Also important, if seldom recognized, is the possibility of the hydrogen bond breaking, as evidenced by physical techniques such as IR, Raman or NMR and caused by loss of hydrogen bond 'covalency' due to electron rearrangement, without any angular change in the O-H····O atomic positions. Thus, clusters may persist for much longer times [329] than common interpretation of data from these methods indicates. Evidence for this may be drawn from the high degree of hydrogen bond breakage seen in the IR spectrum of ice [699], where the clustering is taken as lasting essentially forever. Rearranging hydrogen bonds The molecular orbitals of water indicate that the two 'lone pairs' of electrons do not give distinct directed electron density in isolated molecules, with tetrahedral nature of water's hydrogen bonding due to four-coordination involving two donor and two acceptor hydrogen bonds. However trigonal (approximately planar) hydrogen bonding is also possible with two donor and one acceptor hydrogen bonds associated with individual water molecules. The lack of substantial tetrahedrally positioned 'lone pair' electrons may ease this process, at a cost of one hydrogen bond energy. Also the acceptor hydrogen bond in three coordinated but tetrahedral arrangements (two donor and one acceptor hydrogen bonds with one vacant acceptor site) can slide through a planar arrangement to the vacant tetrahedral site without breaking. This flexibility in the hydrogen bonding topology facilitates hydrogen-bonding rearrangements. Bifurcated hydrogen bonds Bifurcated hydrogen bonds (where both hydrogen atoms from one water molecule are hydrogen bonding to the same other water molecule, or one hydrogen atom simultaneously forms hydrogen bonds to two other water molecules) have just under half the strength of a normal hydrogen bond (per half the bifurcated bond) and present a low-energy route for hydrogen-bonding rearrangements [255]. They allow the constant randomization of the hydrogen bonding within the network. However, it should be noted that they require the breakage of two hydrogen bonds; one hydrogen bond to form the bifurcated arrangement and another to make way for a different hydrogen bond to form. Any necessary rotation may also involve bending or stretching other hydrogen bonds. Bifurcation of hydrogen bonds cannot cause their net breakage and only occur when a broken hydrogen bond releases a lone pair to accept the incoming hydrogen bond donor [1135]. Trifurcated hydrogen bonds (where one hydrogen atom simultaneously forms hydrogen bonds to three other water molecules, forming a tetrahedral face) may also form but only have about one sixth the strength of a normal hydrogen bond per third of the bifurcated bond [573], require free lone pairs on all three bound water molecules and the rest of local cluster must also be poorly hydrogen bonded. Information transfer Hydrogen bonding carries information about solutes and surfaces over significant distances in liquid water. The effect is synergistic, directive and extensive. Thus, in the diagram opposite, strong hydrogen-bonding in molecule (1), caused by solutes or surfaces, will be transmitted to molecules 2 and 3, then to 5 and 6 and then as combined power to 8. The effect is reinforced by additional polarization effects and the resonant intermolecular transfer of O-H vibrational energy, mediated by dipole-dipole interactions and the hydrogen bonds [142]. Reorientation of one molecule induces corresponding motions in the neighbors. Thus solute molecules can 'sense' (for example, effect each others solubility) each other at distances of several nanometers and surfaces may have effects extending to tens of nanometers. This long range correlation of molecular orientation has recently been confirmed using hyper-Rayleigh light scattering [152] and is a reason for the high dielectric constant of water and the consequential reduction in this dielectric constant as the temperature is raised and the number of hydrogen bonds is reduced [239]. Where water molecules are next to flat hydrophobic surfaces, and unable to form extensive clathrate structuring, some hydrogen bonds must be broken and the water molecules will tend to change orientation, from one hydrogen bond directed orthogonally away from the surface (as in clathrates) to one hydrogen bond directed orthogonally towards the surface, in order to minimize the energy requirement. Also the water molecules tend to collapse into their shallow energy minima due to increased non-bonded interactions. Although there may be a consequentially increased density in the first water layer, the second and subsequent water shells compensate by forming stronger hydrogen bonds and a less dense structure. Consequences of this include differential solvation properties affecting surface absorption. Hydrogen bonding rearrangement offers a low energy pathway for the transfer of hydrogen atoms during tautomerism, in a way similar to Grotthuss mechanism for hydrogen ion transport. Shown opposite is adenine tautomerism that can give rise to Adenine - Cytosine (mutation producing) pairing, which uses the rare tautomer on the left. Footnotes a1 This is the energy (ΔH) required for breaking and completely separating the bond, and should equal about half the enthalpy of vaporization. On the same basis ΔS = 37 J deg-1 mol-1 [168]. (Lower enthalpies for the hydrogen bond have been reported [1369], varying between ~6-23 kJ mol-1, with entropies ~29-46 J deg-1 mol-1, depending on the assumptions made ). Just breaking the hydrogen bond in liquid water leaving the molecules essentially in the same position requires only about 25% of this energy; recently estimated at 6.3 kJ mol-1 [690]. If the hydrogen bond energy is determined from the excess heat capacity of the liquid over that of steam (assuming that this excess heat capacity is attributable to the breaking of the bonds) ΔH = 9.80 kJ mol-1 [274]. A number of estimates give the equivalent ΔG at about 2 kJ mol-1 at 25°C [344]; however from the equilibrium content of hydrogen bonds (1.7 mol-1) it is -5.7 kJ mol-1. The hydrogen bonding in ice Ih is about 3 kJ mol-1 stronger than liquid water (= 28 kJ mol-1 at 0 K, from lattice energy including non-bonded interactions) and evidenced by an about 4 pm longer, and hence weaker, O-H covalent bond. Hydrogen bonds in D2O are more linear, shorter [554] and stronger than in H2O and those in T2O are expected to be stronger still. Thus given the choice, hydrogen bonds form with the preference O-T····O > O-D····O > O-H····O. [Back] a2 The average molecular linear translational energy is RT/2. The average collision energy is RT (2.479 kJ mol-1). 2% of collisions have energy greater than the energy required to break the bonds (9.80 kJ mol-1, [274]) as determined by excess heat capacity. [Back] b Unfortunately this is difficult to use as a tool, however, due to the averaging of the shift and the complexity of the system. The spin-lattice relaxation times (T1, ~3.6 s, 25°C) of the water protons is also a function of the hydrogen bonding, being shorter for stronger bonding. The effect of solutes, however, shows the chemical shift and spin-lattice relaxation time are not correlated, as solutes may reduce the extent of hydrogen bonding at the same time as increasing its strength [281]. [Back] c Whether a hydrogen bond is considered broken or just stretched and/or bent should be defined by its strength but, as the isolated bond strength may be difficult to determine, this often remains a matter of definition based on distances and angles. An arrangement with strained geometry is very unlikely to last long. It may, however, occur during the breakage, formation or partner-switching (that is, bifurcation) of a hydrogen bond or arise transiently, due to thermal effects or other molecular interactions, in a long-lived hydrogen bond. The lifetime of a hydrogen bond (if more than 10-13 s) presents another measure of hydrogen bond formation but this also suffers from uncertainties in the definition of its geometry. [Back] c2 Other workers use more generous parameters; for example, in [848], the hydrogen bond length must be less than 3.50 Å and the bond angle greater than 120°. The importance of choosing a correct definition for the hydrogen bonds has been examined [1240]. The simple distance criterion of 2.50 Å for the H····O distance was found very useful and cheapest in computational terms whereas methods based on energy proved poor. Adding further criteria, such as the bond angles, proved of marginal use [1240]. Using simulations, it has been proposed that purely geometric and energetic definitions are inaccurate as they may overestimate the connectivity and lifetime of hydrogen bonds and cannot distinguish improper relative orientations [1335]. Such overestimates may, however, be balanced by underestimates due to the cut-off parameters. [Back] d There is still some controversy surrounding this partial covalency with both for (for example, [411] gives the 3a1 orbital as most responsible for the hydrogen bonding via orbital mixing), against (for example, [437] favors 'antibonding' rather than bonding due to the charge transfer) and neutral [438] in the recent literature. If the water hydrogen bond is considered within the context of the complete range of molecular hydrogen bonding then it appears most probable that it is not solely electrostatic [447]; indeed the continuous transformation of ice VII to ice X would seem to indicate a continuity of electron sharing between water molecules. Although N-H····N and N-H····O hydrogen bonds are known to be weaker than the O-H····O hydrogen bonds in water, there is clear evidence for the bonds' covalent natures from NMR. In nucleic acids, inter-nucleotide N-H····N coupling (2JNN, using 15N nuclei) confirms some covalent nature in the N-H····N hydrogen bond [779]. Also, 3-bond NMR (3JNC) splitting has been found through peptide N-H····O=C hydrogen bonds in proteins, confirming some covalent nature in the N-H····O hydrogen bond [780]. [Back] e The O-H vibrational frequency does not follow the O····O hydrogen bond length exactly due to dispersion of the hydrogen bond O-H····O angle [439]. [Back] f However note that some hydrogen bonds may distort a hydrogen bonded cluster such that when such a bond breaks the detached cluster may form a more optimum tetrahedrally bonded arrangement with lower energy and thus reclaiming some or most of the energy lost by bond breakage. [Back] g The interpretation of the structure of water in terms of strands and rings of doubly-linked hydrogen-bonded molecules [613] was not confirmed by a Compton scattering study [1083] where the data was consistent with 3.9 hydrogen bonds (Roo≤3.2Â) around each water molecule, and has been disputed by another X-ray absorption spectroscopic study [690a], which presents a case for the 'non-, or only weakly, bonded O-H groups' to form the majority of O-H groups present and that these groups are more strongly bonded. Also, Bowron challenges the above interpretation (that is, [613]) in the Discussion included in [746] and a Raman study supports the fully tetrahedrally hydrogen bonded model [875]. This dispute was thought to have been resolved by an ab initio molecular dynamics study [832] that shows 170 fs fluctuations of 2.2-fold strength between the two donor hydrogen bonds from each water molecule whilst the overall geometric connectivity is retained, in line with the hypothesis first presented above. However this study [832] has attracted serious criticism [1159], leaving its conclusions seemingly unproven. Recent ab initio calculations of the x-ray cross section of liquid water shows only 20% broken hydrogen bonds are present [1059] and a novel force field for water, developed from first principles, gives 3.8 shared tetrahedrally coordinated hydrogen bonds per water molecule [1189]. Also, an ab initio quantum mechanical/molecular mechanics molecular dynamics simulation study shows that although the time averaged hydrogen bonding is about four shared hydrogen bonds per water molecule, the instantaneous value is significantly lower at about 2.8 shared hydrogen bonds per water molecule [922]. Tetrahedrally-coordinated water seems most accepted at the present time, but it is clear that a mixture of a minority of higher (4-linked) and a majority of lower (2-linked) hydrogen bond coordinated water can be fitted equally well with the experimental data [1350]. [Back] h The hydrogen bond in water was first suggested by Latimer and Rodebush in 1920 [789]. [Back] i The van der Waals attraction has been estimated as high as about 5.5 kJ mol-1 [548] based on isoelectronic molecules at optimal separation, but is likely to be repulsive within a hydrogen bond due to the close contact (see for example, [736]). Separating the hydrogen bond components, as below, helps our understanding, although in reality these components are combined. Attraction/repulsion ++ electrostatic attraction long range interaction (< 30 Å) based on point charges, or on dipoles plus quadrupoles, and so on. They may be considered as varying with distance-1. ++ polarization attraction due to net attractive effects between charges and electron clouds (< 8 Å), which may increase cooperatively dependent on the local environment. They may be considered as varying with distance-4. This net attractive effect may contain a small repulsive element due to slightly increased electron cloud overlap. + covalency attraction highly directional and increases on hydrogen bonded cyclic cluster formation. It is very dependent on the spatial arrangement of the molecules within the local environment (< 6 Å) + dispersive attraction interaction (< 6 Å) due to coordinated effects of neighboring electron clouds. They may be considered as varying with distance-6. -- electron repulsion very short range interaction (< 4 Å) due to electron cloud overlap. They may be considered as varying with distance-12. [Back] j In an unstrained tetrahedral network (such as ice Ih) only the six structures below can arise with no structures at intermediate angles. The hydrogen bond energy depends particularly on the angle of rotation around the hydrogen bond, as below, due to the interaction between the molecular dipoles. Note that the hydrogen bonds in the structure pairs (a) and (e), and (b) and (d) have identical energies. In ice Ih with no net dipole moment, the configurations with extreme cis/trans ratios have 56.3% cis (i.e. a+e+f) or 64.7% trans (that is, b+c+d) but the calculated difference in energies was only 0.12% (0.06 kJ mol-1) [858]; much lower than the expected (several kJ mol-1) difference in energy between trans and cis structures c and f. As a, c and e involve protons in hydrogen bonds parallel to the c-axis, their increased strength relative to b, d and f may be causative to the (0.3%) shortened c-axis in the ice Ih unit cell.

Recent reviews in Organic chemistry

Recent Reviews Reviews are listed in order of appearance in the sources indicated. In multidisciplinary review journals, only those reviews which fall within the scope of this Journal are included. Sources are listed alphabetically in three categories: regularly issued review journals and series volumes, contributed volumes, and other monographs. Titles are numbered serially, and these numbers are used for reference in the index. Major English-language sources of critical reviews are covered. Encyclopedic treatises, annual surveys such as Specialist Periodical Reports, and compilations of symposia proceedings are omitted. This installment of Recent Reviews covers principally the middle part of the 2004 literature. Previous installment: J. Org. Chem. 2004, 69(20), 6957-66. Supporting Information Available: A file containing this Recent Review compilation in Microsoft Word and the data in plain text that can be imported into Endnote (using Refer style) and Reference Manager databases. This material is available free of charge via the Internet at http://pubs.acs.org. Regularly Issued Journals and Series Volumes Accounts of Chemical Research 1. Jia, G. Progress in the Chemistry of Metallabenzynes. 2004, 37(7), 479-86. 2. Houk, K. N.; List, B. Asymmetric Organocatalysis. 2004, 37(8), 487. 3. Shi, Y. Organocatalytic Asymmetric Epoxidation of Olefins by Chiral Ketones. 2004, 37(8), 488-96. 4. Yang, D. Ketone-Catalyzed Asymmetric Epoxidation Reactions. 2004, 37(8), 497-505. 5. O'Donnell, M. J. The Enantioselective Synthesis of a-Amino Acids by Phase-Transfer Catalysis with Achiral Schiff Base Esters. 2004, 37(8), 506-17. 6. Lygo, B.; Andrews, B. I. Asymmetric Phase-Transfer Catalysis Utilizing Chiral Quaternary Ammonium Salts: Asymmetric Alkylation of Glycine Imines. 2004, 37(8), 518-25. 7. Ooi, T.; Maruoka, K. Asymmetric Organocatalysis of Structurally Well-Defined Chiral Quaternary Ammonium Fluorides. 2004, 37(8), 526-33. 8. Enders, D.; Balensiefer, T. Nucleophilic Carbenes in Asymmetric Organocatalysis. 2004, 37(8), 534-41. 9. Fu, G. C. Asymmetric Catalysis with "Planar-Chiral" Derivatives of 4-(Dimethylamino)pyridine. 2004, 37(8), 542-7. 10. List, B. Enamine Catalysis is a Powerful Strategy for the Catalytic Generation and Use of Carbanion Equivalents. 2004, 37(8), 548-57. 11. Allemann, C.; Gordillo, R.; Clemente, F. R.; Cheong, P. H.-Y.; Houk, K. N. Theory of Asymmetric Organocatalysis of Aldol and Related Reactions: Rationalizations and Predictions. 2004, 37(8), 558-69. 12. Saito, S.; Yamamoto, H. Design of Acid-Base Catalysis for the Asymmetric Direct Aldol Reaction. 2004, 37(8), 570-9. 13. Notz, W.; Tanaka, F.; Barbas, C. F., III Enamine-Based Organocatalysis with Proline and Diamines: The Development of Direct Catalytic Asymmetric Aldol, Mannich, Michael, and Diels-Alder Reactions. 2004, 37(8), 580-91. 14. France, S.; Weatherwax, A.; Taggi, A. E.; Lectka, T. Advances in the Catalytic, Asymmetric Synthesis of b-Lactams. 2004, 37(8), 592-600. 15. Miller, S. J. In Search of Peptide-Based Catalysts for Asymmetric Organic Synthesis. 2004, 37(8), 601-10. 16. Aggarwal, V. K.; Winn, C. L. Catalytic, Asymmetric Sulfur Ylide-Mediated Epoxidation of Carbonyl Compounds: Scope, Selectivity, and Applications in Synthesis. 2004, 37(8), 611-20. 17. Tian, S.-K.; Chen, Y.; Hang, J.; Tang, L.; McDaid, P.; Deng, L. Asymmetric Organic Catalysis with Modified Cinchona Alkaloids. 2004, 37(8), 621-31. 18. Gridnev, I. D.; Imamoto, T. On the Mechanism of Stereoselection in Rh-Catalyzed Asymmetric Hydrogenation: A General Approach for Predicting the Sense of Enantioselectivity. 2004, 37(9), 633-44. 19. Deubel, D. V.; Frenking, G.; Gisdakis, P.; Herrmann, W. A.; Roesch, N.; Sundermeyer, J. Olefin Epoxidation with Inorganic Peroxides. Solutions to Four Long-Standing Controversies on the Mechanism of Oxygen Transfer. 2004, 37(9), 645-52. 20. Jang, H.-Y.; Krische, M. J. Catalytic C-C Bond Formation via Capture of Hydrogenation Intermediates. 2004, 37(9), 653-61. 21. Hong, S.; Marks, T. J. Organolanthanide-Catalyzed Hydroamination. 2004, 37(9), 673-86. 22. Wasserman, H. H.; Parr, J. The Chemistry of Vicinal Tricarbonyls and Related Systems. 2004, 37(9), 687-701. 23. Braese, S. The Virtue of the Multifunctional Triazene Linkers in the Efficient Solid-Phase Synthesis of Heterocycle Libraries. 2004, 37(10), 804-15. 24. Barbero, A.; Pulido, F. J. Allylsilanes and Vinylsilanes from Silylcupration of Carbon-Carbon Multiple Bonds: Scope and Synthetic Applications. 2004, 37(10), 816-24. Advances in Carbohydrate Chemistry and Biochemistry 25. Plante, O. J.; Palmacci, E. R.; Seeberger, P. H. Development of an Automated Oligosaccharide Synthesizer. 2003, 58, 35-54. 26. Knirel, Y. A.; Shashkov, A. S.; Tsvetkov, Y. E.; Jansson, P.-E.; Zaehringer, U. 5,7-Diamino-3,5,7,9-tetradeoxy-non-2-ulosonic Acids in Bacterial Glyco-polymers: Chemistry and Biochemistry. 2003, 58, 371-417. Advances in Heterocyclic Chemistry 27. El-Ashry, E.-S. H.; Ibrahim, E.-S. I. Fused Heterocyclo-Quinolines Containing one Nitrogen Atom at Ring Junction: Part 1. Four and Five Membered Heterocyclo-Quinolines. 2003, 84, 71-190. 28. Sadimenko, A. P. Organometallic Complexes of Boron, Silicon, and Phosphorus Analogs of Azoles. 2003, 85, 1-66. 29. Hermecz, I. Recent Developments in the Chemistry of Pyridooxazines, Pyridothiazines, Pyridodiazines and Their Benzologs. Part 2. 2003, 85, 173-285. 30. Sadimenko, A. P. Organometallic Complexes of Pyridines and Benzannulated Pyridines. 2004, 86, 293-343. Advances in Organometallic Chemistry 31. Kost, D.; Kalikhman, I. Hydrazide-Based Hypercoordinate Silicon Compounds. 2004, 50, 1-106. 32. Yoo, B. R.; Jung, I. N. Synthesis of Organosilicon Compounds by New Direct Reactions. 2004, 50, 145-77. 33. Bruce, M. I.; Low, P. J. Transition Metal Complexes Containing All-Carbon Ligands. 2004, 50, 179-444. Angewandte Chemie, International Edition in English 34. Marco-Contelles, J. b-Lactam Synthesis by the Kinugasa Reaction. 2004, 43(17), 2198-200. 35. Miura, M. Rational Ligand Design in Constructing Efficient Catalyst Systems for Suzuki-Miyaura Coupling. 2004, 43(17), 2201-3. 36. Brunner, H. A New Hydrosilylation Mechanism - New Preparative Opportunities. 2004, 43(21), 2749-50. 37. Merino, P.; Tejero, T. Organocatalyzed Asymmetric a-Aminoxylation of Aldehydes and Ketones - An Efficient Access to Enantiomerically Pure a-Hydroxycarbonyl Compounds, Diols, and Even Amino Alcohols. 2004, 43(23), 2995-7. 38. Koehn, M.; Breinbauer, R. The Staudinger Ligation - A Gift to Chemical Biology. 2004, 43(24), 3106-16. 39. Graening, T.; Schmalz, H.-G. Total Synthesis of Colchicine in Comparison: A Journey Through 50 Years of Synthetic Organic Chemistry. 2004, 43(25), 3230-56. 40. Glorius, F. Chiral Olefin Ligands - New "Spectators" in Asymmetric Catalysis. 2004, 43(26), 3364-6. 41. Beller, M.; Seayad, J.; Tillack, A.; Jiao, H. Catalytic Markovnikov and Anti-Markovnikov Functionalization of Alkenes and Alkynes. Recent Developments and Trends. 2004, 43(26), 3368-98. 42. Stahl, S. S. Palladium Oxidase Catalysis. Selective Oxidation of Organic Chemicals by Direct Dioxygen-Coupled Turnover. 2004, 43(26), 3400-20. 43. Gonda, J. The Bellus-Claisen Rearrangement. 2004, 43(27), 3516-24. 44. Ajamian, A.; Gleason, J. L. Two Birds with One Metallic Stone: Single-Pot Catalysis of Fundamentally Different Transformations. 2004, 43(29), 3754-60. 45. Rosenthal, U. Stable Cyclopentynes - Made by Metals!? 2004, 43(30), 3882-7. 46. Montgomery, J. Nickel-Catalyzed Reductive Cyclizations and Couplings. 2004, 43(30), 3890-908. Chemical Reviews 47. Kovbasyuk, L.; Kraemer, R. Allosteric Supramolecular Receptors and Catalysts. 2004, 104(6), 3161-87. 48. Zuman, P. Reactions of Ortho-Phthalaldehyde with Nucleophiles. 2004, 104(7), 3217-38. 49. Gowenlock, B. G.; Richter-Addo, G. B. Preparations of C-Nitroso Compounds. 2004, 104(7), 3315-40. 50. Chrzanowska, M.; Rozwadowska, M. D. Asymmetric Synthesis of Isoquinoline Alkaloids. 2004, 104(7), 3341-70. 51. Edmonds, D. J.; Johnston, D.; Procter, D. J. Samarium(II)-Iodide-Mediated Cyclizations in Natural Product Synthesis. 2004, 104(7), 3371-403. 52. Tietze, L. F.; Ila, H.; Bell, H. P. Enantioselective Palladium-Catalyzed Transformations. 2004, 104(7), 3453-516. 53. McManus, H. A.; Guiry, P. J. Recent Developments in the Application of Oxazoline-Containing Ligands in Asymmetric Catalysis. 2004, 104(9), 4151-202. Chemical Society Reviews 54. Perez, D.; Guitian, E. Selected Strategies for the Synthesis of Triphenylenes. 2004, 33(5), 274-83. 55. Alonso, F.; Yus, M. The NiCl2-Li-Arene(cat.) Combination: A Versatile Reducing Mixture. 2004, 33(5), 284-93. 56. Moriuchi, T.; Hirao, T. Highly Ordered Structures of Peptides by Using Molecular Scaffolds. 2004, 33(5), 294-301. 57. Lee, J. M.; Na, Y.; Han, H.; Chang, S. Cooperative Multi-Catalyst Systems for One-Pot Organic Transformations. 2004, 33(5), 302-12. 58. Atkinson, R. C. J.; Gibson, V. C.; Long, N. J. The Syntheses and Catalytic Applications of Unsymmetrical Ferrocene Ligands. 2004, 33(5), 313-28. 59. Chankvetadze, B. Combined Approach Using Capillary Electrophoresis and NMR Spectroscopy for an Understanding of Enantioselective Recognition Mechanisms by Cyclodextrins. 2004, 33(6), 337-47. 60. French, A. N.; Bissmire, S.; Wirth, T. Iodine Electrophiles in Stereoselective Reactions: Recent Developments and Synthetic Applications. 2004, 33(6), 354-62. Chemistry - A European Journal 61. Bullock, R. M. Catalytic Ionic Hydrogenations. 2004, 10(10), 2366-74. 62. Malinakova, H. C. Chiral Nonracemic Late-Transition-Metal Organometallics with a Metal-Bonded Stereogenic Carbon Atom: Development of New Tools for Asymmetric Organic Synthesis. 2004, 10(11), 2636-46. 63. Ding, K.; Du, H.; Yuan, Y.; Long, J. Combinatorial Chemistry Approach to Chiral Catalyst Engineering and Screening: Rational Design and Serendipity. 2004, 10(12), 2872-84. 64. Yoshida, M.; Ihara, M. Novel Methodologies for the Synthesis of Cyclic Carbonates. 2004, 10(12), 2886-93. 65. Easton, C. J.; Lincoln, S. F.; Barr, L.; Onagi, H. Molecular Reactors and Machines: Applications, Potential, and Limitations. 2004, 10(13), 3120-8. 66. Dandapani, S.; Curran, D. P. Separation-Friendly Mitsunobu Reactions: A Microcosm of Recent Developments in Separation Strategies. 2004, 10(13), 3130-8. Chemistry of Heterocyclic Compounds 67. Mochalov, S. S.; Gazzaeva, R. A. Arylcyclopropanes in the Synthesis of Nitrogen- and Oxygen-Containing Heterocycles. (Review). 2003, 39(8), 975-88. 68. Abele, E.; Abele, R.; Lukevics, E. Pyrrole Oximes: Synthesis, Reactions, and Biological Activity. Review. 2004, 40(1), 1-15. 69. Zalesov, V. V.; Rubtsov, A. E. Synthesis, Structure, and Chemical Properties of N-Substituted 2(3)-Imino-2,3-Dihydrofuran-3(2)-Ones. Review. 2004, 40(2), 133-53. 70. Shvekhgeimer, M. G. A. The Pfitzinger Reaction. Review. 2004, 40(3), 257-94. CHEMTRACTS: Organic Chemistry 71. Manyem, S.; Zimmerman, J.; Patil, K.; Sibi, M. P. Tin-Free Radical-Mediated C-C Bond Formations. 2003, 16(14), 819-26. 72. Kellogg, R. M. Synthesis of 2,6-Bridged Piperazin-3-Ones by N-Acyliminium Ion Chemistry. 2003, 16(14), 838-42. 73. Guo, H.-C.; Ding, K.; Dai, L.-X. A New Principle in Combinatorial Asymmetric Transition-Metal Catalysis: Mixtures of Chiral Monodentate P Ligands. 2004, 17(2), 57-66. 74. Risatti, C. A.; Taylor, R. E. Biomimetic Synthesis of Polycyclic Natural Products from Acyclic Precursors. 2004, 17(2), 83-91. 75. Iyengar, R.; Gracias, V. Asymmetric Total Synthesis of (+)-Sparteine and the Synthesis of a Readily Accessible (+)-Sparteine Surrogate. 2004, 17(2), 92-6. 76. Madec, D.; Poli, G. Unusual Regioselectivities in Palladium-Catalyzed Allylic Substitution. 2004, 17(2), 104-14. Collection of Czechoslovak Chemical Communications 77. Klein, M.; Walenzyk, T.; Koenig, B. Electronic Effects on the Bergman Cyclisation of Enediynes. A Review. 2004, 69(5), 945-65. 78. Parola, S.; Desroches, C. Recent Advances in the Functionalizations of the Upper Rims of Thiacalix[4]Arenes. A Review. 2004, 69(5), 966-83. 79. Pulpoka, B.; Vicens, J. 1,3-Alternate Calix[4]Arene: The Sophisticated Conformer of Calix[4]Arene. A Review. 2004, 69(6), 1251-81. 80. Svozil, D.; Jungwirth, P.; Havlas, Z. Electron Binding to Nucleic Acid Bases. Experimental and Theoretical Studies. A Review. 2004, 69(7), 1395-428. Coordination Chemistry Reviews 81. Herndon, J. W. The Chemistry of the Carbon-Transition Metal Double and Triple Bond: Annual Survey Covering the Year 2002. 2004, 248(1-2), 3-79. 82. Peris, E. From Long-Chain Conjugated Oligomers to Dendrimers: Synthesis and Physical Properties of Phenyl-Ethenyl-Ferrocenyl Containing One- and Two-Dimensional Complexes. 2004, 248(3-4), 279-97. 83. Fox, M. A.; Hughes, A. K. Cage C-H···X Interactions in Solid-State Structures of Icosahedral Carboranes. 2004, 248(5-6), 457-76. 84. Oh, M.; Reingold, J. A.; Carpenter, G. B.; Sweigart, D. A. Manganese Tricarbonyl Transfer (MTT) Reagents in the Construction of Novel Organometallic Systems. 2004, 248(7-8), 561-9. 85. Kudinov, A. R.; Mutseneck, E. V.; Loginov, D. A. (Tetramethylcyclobutadiene)cobalt Chemistry. 2004, 248(7-8), 571-85. 86. Jin, G.-X. Advances in the Chemistry of Organometallic Complexes with 1,2-Dichalcogenolato-O-Carborane Ligands. 2004, 248(7-8), 587-602. 87. Balazs, L.; Breunig, H. J. Organometallic Compounds with Sb-Sb or Bi-Bi Bonds. 2004, 248(7-8), 603-21. 88. Cavell, K. J.; McGuinness, D. S. Redox Processes Involving Hydrocarbylmetal (N-Heterocyclic Carbene) Complexes and Associated Imidazolium Salts: Ramifications for Catalysis. 2004, 248(7-8), 671-81. 89. Ceccon, A.; Santi, S.; Orian, L.; Bisello, A. Electronic Communication in Heterobinuclear Organometallic Complexes Through Unsaturated Hydrocarbon Bridges. 2004, 248(7-8), 683-724. 90. Harman, W. D. Conformational and Linkage Isomerizations for Dihapto-Coordinated Arenes and Aromatic Heterocycles: Controlling the Stereochemistry of Ligand Transformations. 2004, 248(9-10), 853-66. 91. Richmond, M. G. Annual Survey of Organometallic Metal Cluster Chemistry for the Year 2002. 2004, 248(9-10), 881-901. Current Medicinal Chemistry 92. Shuto, S.; Matsuda, A. Chemistry of Cyclic ADP-Ribose and Its Analogs. 2004, 11(7), 827-45. 93. Gunaga, P.; Moon, H. R.; Choi, W. J.; Shin, D. H.; Park, J. G.; Jeong, L. S. Recent Advances in 4'-Thionucleosides as Potential Antiviral and Antitumor Agents. 2004, 11(19), 2585-637. Current Organic Chemistry 94. Quideau, S.; Pouysegu, L.; Deffieux, D. Chemical and Electrochemical Oxidative Activation of Arenol Derivatives for Carbon-Carbon Bond Formation. 2004, 8(2), 113-48. 95. Sabatino, G.; Chelli, M.; Brandi, A.; Papini, A. M. Analytical Methods for Solid Phase Peptide Synthesis. 2004, 8(4), 291-301. 96. Harvey, R. G. Advances in the Synthesis of Polycyclic Aromatic Compounds. 2004, 8(4), 303-23. 97. Furman, B.; Borsuk, K.; Kaluza, Z.; Lysek, R.; Chmielewski, M. Stereochemistry of [2+2]Cycloaddition of Chlorosulfonyl Isocyanate to Olefins. 2004, 8(6), 463-73. 98. Corsaro, A.; Chiacchio, U.; Pistara, V.; Romeo, G. Microwave-Assisted Chemistry of Carbohydrates. 2004, 8(6), 511-38. 99. Taylor, C. M.; Watson, A. J. The Anionic Phospho-Fries Rearrangement. 2004, 8(7), 623-36. 100. Schmidt, A. Biologically Active Mesomeric Betaines and Alkaloids, Derived from 3-Hydroxypyridine, Pyridin-N-Oxide, Nicotinic Acid and Picolinic Acid: Three Types of Conjugation and Their Consequences. 2004, 8(8), 653-70. 101. Cruz, A.; Juarez-Juarez, M. Heterocyclic Compounds Derived from Ephedrines. 2004, 8(8), 671-93. 102. Milan, M.; Viktor, M.; Rudolf, K.; Dusan, I. Preparation of Cyclic 1,3-Diketones and Their Exploitation in the Synthesis of Heterocycles. 2004, 8(8), 695-714. 103. Lavilla, R. Non-Conventional Redox Chemistry of Dihydropyridines and Pyridinium Salts. 2004, 8(8), 715-37. 104. Phillips, D. L.; Fang, W. H.; Zheng, X.; Li, Y. L.; Wang, D.; Kwok, W. M. Isopolyhalomethanes. Their Formation, Structures, Properties and Cyclopropanation Reactions with Olefins. 2004, 8(9), 739-55. 105. Zhang, W. Recent Advances in the Synthesis of Biologically Interesting Heterocycles by Intramolecular Aryl Radical Reactions. 2004, 8(9), 757-80. 106. Guiry, P. J.; Kiely, D. The Development of the Intramolecular Asymmetric Heck Reaction. 2004, 8(9), 781-94. 107. Honda, E.; Kataoka, T. Chemistry of Selenabenzenes and Related Compounds. 2004, 8(9), 813-25. 108. Arques, A.; Molina, P. Bis(iminophosphoranes) as Useful Building Blocks for the Preparation of Complex Polyaza Ring Systems. 2004, 8(9), 827-43. 109. De La Hoz, A.; Diaz-Ortiz, A.; Moreno, A. Selectivity in Organic Synthesis under Microwave Irradiation. 2004, 8(10), 903-18. 110. Gabriele, B.; Salerno, G.; Costa, M.; Chiusoli, G. P. Recent Advances in the Synthesis of Carbonyl Compounds by Palladium-Catalyzed Oxidative Carbonylation Reactions of Unsaturated Substrates. 2004, 8(10), 919-46. 111. Soriente, A.; De Rosa, M.; Villano, R.; Scettri, A. Recent Advances in Asymmetric Aldol Reaction of Masked Acetoacetic Esters Promoted by Ti(IV)/Binol. A New Methodology, Non-Linear Effects and Autoinduction. 2004, 8(11), 993-1007. 112. Tanaka, H.; Kuroboshi, M. Aluminium as an Electron Pool for Organic Synthesis. Multi-Metal Redox-Promoted Reactions. 2004, 8(11), 1027-56. 113. Mihovilovic, M. D.; Rudroff, F.; Groetzl, B. Enantioselective Baeyer-Villiger Oxidations. 2004, 8(12), 1057-69. 114. Yranzo, G. I.; Moyano, E. L. Flash Vacuum Pyrolysis of Isoxazoles, Pyrazoles and Related Compounds. 2004, 8(12), 1071-88. 115. Gueltekin, M. S.; Celik, M.; Balci, M. Cyclitols. Conduritols and Related Compounds. 2004, 8(13), 1159-86. 116. Sliwa, W.; Girek, T.; Koziol, J. J. Cyclodextrin Oligomers. 2004, 8(15), 1445-62. Current Organic Synthesis 117. Kirsch, G.; Hesse, S.; Comel, A. Synthesis of Five- and Six-Membered Heterocycles Through Palladium-Catalyzed Reactions. 2004, 1(1), 47-63. 118. Avendano, C.; Menendez, J. C. Synthetic Studies on N-Methylwelwitindolinone C Isothiocyanate (Welwistatin) and Related Substructures. 2004, 1(1), 65-82. 119. Felpin, F.-X.; Lebreton, J. Synthesis of 2,6-Dialkyl-1,2,5,6-Tetrahydropyridines and Their Applications in Total Synthesis. 2004, 1(1), 83-109. 120. Sineriz, F.; Thomassigny, C.; Lou, J.-D. Recent Advances in Solvent-Free Oxidation of Alcohols. 2004, 1(2), 137-54. 121. Szatmari, I.; Fueloep, F. Syntheses and Transformations of 1-(-Aminobenzyl)-2-naphthol Derivatives. 2004, 1(2), 155-65. 122. Spivey, A. C.; Gripton, C. J. G.; Hannah, J. P. Recent Advances in Group 14 Cross-Coupling: Si and Ge-Based Alternatives to the Stille Reaction. 2004, 1(3), 211-26. 123. Peppe, C. Indium(I) Compounds in Organic Synthesis. 2004, 1(3), 227-31. Current Topics in Medicinal Chemistry 124. Breining, S. R. Recent Developments in the Synthesis of Nicotinic Acetylcholine Receptor Ligands. 2004, 4(6), 609-29. 125. Clarke, D.; Ali, M. A.; Clifford, A. A.; Parratt, A.; Rose, P.; Schwinn, D.; Bannwarth, W.; Rayner, C. M. Reactions in Unusual Media. 2004, 4(7), 729-71. 126. Gao, Z.-G.; Jacobson, K. A. Partial Agonists for A3 Adenosine Receptors. 2004, 4(8), 855-62. 127. Press, N. J.; Keller, T. H.; Tranter, P.; Beer, D.; Jones, K.; Faessler, A.; Heng, R.; Lewis, C.; Howe, T.; Gedeck, P.; Mazzoni, L.; Fozard, J. R. New Highly Potent and Selective Adenosine A3 Receptor Antagonists. 2004, 4(8), 863-70. Heteroatom Chemistry 128. Bansal, R. K.; Gupta, N.; Gupta, N. Cycloaddition Reactions of Heterophospholes. 2004, 15(3), 271-87. Journal of Combinatorial Chemistry 129. Maltais, R.; Tremblay, M. R.; Ciobanu, L. C.; Poirier, D. Steroids and Combinatorial Chemistry. 2004, 6(4), 443-56. 130. Gaggini, F.; Porcheddu, A.; Reginato, G.; Rodriquez, M.; Taddei, M. Colorimetric Tools for Solid-Phase Organic Synthesis. 2004, 6(5), 805-10. Journal of Fluorine Chemistry 131. Yoneda, N. Advances in the Preparation of Organofluorine Compounds Involving Iodine and/or Iodo Compounds. 2004, 125(1), 7-17. 132. Conte, L.; Gambaretto, G. Electrochemical Fluorination: State of the Art and Future Tendencies. 2004, 125(2), 139-44. 133. Taylor, R. Why Fluorinate Fullerenes? 2004, 125(3), 359-68. 134. Dolensky, B.; Nam, G.; Deng, W.-P.; Narayanan, J.; Fan, J.; Kirk, K. L. Syntheses of Side-Chain Fluorinated Biologically Important Imidazoles and Indoles. 2004, 125(4), 501-8. 135. Grobe, J.; Le Van, D. The Chemistry of Fluorine Containing Phosphaalkenes, Arsaalkenes and Selenocarbonyls. 2004, 125(6), 801-21. 136. Tyrra, W.; Naumann, D. Perfluoroorganosilver(I) Compounds. 2004, 125(6), 823-30. 137. Lentz, D. Organometallic Chemistry of Fluorinated Propadienes and Butadienes. 2004, 125(6), 853-61. 138. Borrmann, T.; Lork, E.; Mews, R.; Stohrer, W.-D. Fluoride Ion Transfer and Stabilization of Reactive Ions. 2004, 125(6), 903-16. 139. von Ahsen, S.; Willner, H.; Arguello, G. A. Fluorocarbon Oxy and Peroxy Radicals. 2004, 125(7), 1057-70. Journal of Organometallic Chemistry 140. de Meijere, A.; Kozhushkov, S. I.; Savchenko, A. I. Titanium-Mediated Syntheses of Cyclopropylamines. 2004, 689(12), 2033-55. 141. Thoonen, S. H. L.; Deelman, B.-J.; Van Koten, G. Synthetic Aspects of Tetraorganotins and Organotin(IV) Halides. 2004, 689(13), 2145-57. 142. Danks, T. N.; Wagner, G. The Chemistry of (1-Azabuta-1,3-diene)tricarbonyliron(0) Complexes. 2004, 689(15), 2543-57. Journal of Physical Organic Chemistry 143. Adam, W.; Diedering, M.; Trofimov, A. V. Intriguing Double-Inversion Stereochemistry in the Denitrogenation of 2,3-Diazabicyclo[2.2.1]heptene-type Azoalkanes: A Model Mechanistic Study in Physical Organic Chemistry. 2004, 17(8), 643-55. Journal of the Brazilian Chemical Society 144. Gielen, M. An Overview of Forty Years Organotin Chemistry Developed at the Free Universities of Brussels ULB and VUB. 2003, 14(6), 870-7. Natural Product Reports 145. Draeger, B. Chemistry and Biology of Calystegines. 2004, 21(2), 211-23. 146. Somei, M.; Yamada, F. Simple Indole Alkaloids and Those with a Nonrearranged Monoterpenoid Unit. 2004, 21(2), 278-311. 147. Bentley, K. W. b-Phenylethylamines and the Isoquinoline Alkaloids. 2004, 21(3), 395-424. New Journal of Chemistry 148. Buchmeiser, M. R. Recent Advances in the Synthesis of Supported Metathesis Catalysts. 2004, 28(5), 549-57. 149. Pineschi, M. Copper-Catalyzed Enantioselective Allylic Alkylation Ring-Opening Reactions of Small-Ring Heterocycles with Hard Alkyl Metals. 2004, 28(6), 657-65. 150. Nelson, A. The Development of Strategies and Methods for the Synthesis of Biologically Active Compounds. 2004, 28(7), 771-6. Organic Preparations and Procedures International 151. Hajipour, A. R.; Khoee, S.; Ruoho, A. E. Regeneration of Carbonyl Compounds from Oximes, Hydrazones, Semicarbazones, Acetals, 1,1-Diacetates, 1,3-Dithiolanes, 1,3-Dithianes and 1,3-Oxathiolanes. 2003, 35(6), 527-81. 152. Kotali, A.; Harris, P. A. o-Diacylbenzenes in Organic Synthesis. A Review. 2003, 35(6), 583-601. 153. Merbouh, N.; Bobbitt, J. M.; Brueckner, C. Preparation of Tetramethylpiperidine-1-oxoammonium Salts and Their Use as Oxidants in Organic Chemistry. A Review. 2004, 36(1), 3-31. 154. Tejedor, D.; Garcia-Tellado, F. Synthesis and Chemistry of Tetronic Acids. 2004, 36(1), 35-59. Pure and Applied Chemistry 155. Helmchen, G.; Ernst, M.; Paradies, G. Application of Allylic Substitutions in Natural Products Synthesis. 2004, 76(3), 495-506. 156. Jun, C.-H.; Lee, J. H. Application of C-H and C-C Bond Activation in Organic Synthesis. 2004, 76(3), 577-87. 157. Malachowski, L.; Stair, J. L.; Holcombe, J. A. Immobilized Peptides/Amino Acids on Solid Supports for Metal Remediation. 2004, 76(4), 777-87. 158. Karolak-Wojciechowska, J.; Fruzinski, A. Spacer Conformation in Biologically Active Molecules. 2004, 76(5), 959-64. 159. Dallinger, D.; Stadler, A.; Kappe, C. O. Solid- and Solution-Phase Synthesis of Bioactive Dihydropyrimidines. 2004, 76(5), 1017-24. Russian Journal of Organic Chemistry 160. Moskvin, A. V.; Reznikova, N. R.; Ivin, B. A. Hydroxypyrimidines Condensation with Carbonyl Compounds. Part II. Hydroxy-, Sulfanyl-, and Aminopyrimidines. 2004, 40(2), 143-61. 161. Bukharov, S. V.; Nugumanova, G. N.; Mukmeneva, N. A.; Burilov, A. R.; Kasymova, E. M.; Pudovik, M. A.; Konovalov, A. I. Synthesis of Sterically Hindered Phenols on the Basis of 3,5-Di-tert-butyl-4-hydroxybenzyl Acetate. 2004, 40(3), 293-300. 162. Koldobskii, G. I.; Hrabalek, A.; Esikov, K. A. 1-Substituted 5-Alkyl(aryl)sulfanyltetrazoles and Their Derivatives. 2004, 40(4), 447-61. Science 163. Xie, S.-Y.; Gao, F.; Lu, X.; Huang, R.-B.; Wang, C.-R.; Zhang, X.; Liu, M.-L.; Deng, S.-L.; Zheng, L.-S. Capturing the Labile Fullerene[50] as C50Cl10. 2004, 304(5671), 699. 164. Smith, R. R.; Killelea, D. R.; DelSesto, D. F.; Utz, A. L. Preference for Vibrational over Translational Energy in a Gas-Surface Reaction. 2004, 304(5673), 992-5. 165. Kobayashi, J.; Mori, Y.; Okamoto, K.; Akiyama, R.; Ueno, M.; Kitamori, T.; Kobayashi, S. A Microfluidic Device for Conducting Gas-Liquid-Solid Hydrogenation Reactions. 2004, 304(5675), 1305-8. 166. Wang, L.; Vysotsky, M. O.; Bogdan, A.; Bolte, M.; Boehmer, V. Multiple Catenanes Derived from Calix[4]arenes. 2004, 304(5675), 1312-4. 167. Miyashita, M.; Sasaki, M.; Hattori, I.; Sakai, M.; Tanino, K. Total Synthesis of Norzoanthamine. 2004, 305(5683), 495-9. 168. Bertrand, G. Chemistry: The Modest Undressing of a Silicon Center. 2004, 305(5685), 783-5. 169. Jutzi, P.; Mix, A.; Rummel, B.; Schoeller, W. W.; Neumann, B.; Stammler, H.-G. The (Me5C5)Si+ Cation: A Stable Derivative of HSi+. 2004, 305(5685), 849-51. Sulfur Reports 170. Abu-Yousef, I. A.; Harpp, D. N. New Sulfenyl Chloride Chemistry: Synthesis, Reactions and Mechanisms toward Carbon-Carbon Double Bonds. 2003, 24(3), 255-82. 171. Tandon, V. K.; Rai, S. p-Toluenesulfonylmethyl Isocyanide: a Versatile Synthon in Organic Chemistry. 2003, 24(3), 307-85. Synlett 172. Das, S. K. Application of Microwave Irradiation in the Synthesis of Carbohydrates. 2004, (6), 915-32. 173. Byrne, L. A.; Gilheany, D. G. Simple Syntheses of Seven-Membered Rings via an Entropy/Strain Reduction Strategy. 2004, (6), 933-43. 174. Matyus, P.; Maes, B. U. W.; Riedl, Z.; Hajos, G.; Lemiere, G. L. F.; Tapolcsanyi, P.; Monsieurs, K.; Elias, O.; Dommisse, R. A.; Krajsovszky, G. New Pathways Towards Pyridazino-Fused Ring Systems. 2004, (7), 1123-39. 175. Miyabe, H.; Ueda, M.; Naito, T. Carbon-Carbon Bond Construction Based on Radical Addition to C=N Bond. 2004, (7), 1140-57. 176. Geng, X.; Yang, Z.-Q.; Danishefsky, S. J. Synthetic Development of Radicicol and Cycloproparadicicol: Highly Promising Anticancer Agents Targeting Hsp90. 2004, (8), 1325-33. 177. Belvisi, L.; Colombo, L.; Manzoni, L.; Potenza, D.; Scolastico, C. Design, Synthesis, Conformational Analysis and Application of Azabicycloalkane Amino Acids as Constrained Dipeptide Mimics. 2004, (9), 1449-71. 178. Bonifacio, V. D. B. Meldrum's Acid. 2004, (9), 1649-50. 179. Adak, A. K. Phenyl Dichlorophosphate - A Versatile Reagent. 2004, (9), 1651-2. Synthesis-Stuttgart 180. Grasa, G. A.; Singh, R.; Nolan, S. P. Transesterification/Acylation Reactions Catalyzed by Molecular Catalysts. 2004, (7), 971-85. 181. Gravel, M.; Lachance, H.; Lu, X.; Hall, D. G. Scope and Limitations of the Scandium-Catalyzed Enantioselective Addition of Chiral Allylboronates to Aldehydes. 2004, (8), 1290-302. 182. Wu, Q.; Simons, C. Synthetic Methodologies for C-Nucleosides. 2004, (10), 1533-53. Tetrahedron 183. Pellissier, H. The Glycosylation of Steroids. 2004, 60(24), 5123-62. 184. Ranganathan, S.; Muraleedharan, K. M.; Vaish, N. K.; Jayaraman, N. Halo- and Selenolactonization: The Two Major Strategies for Cyclofunctionalization. 2004, 60(25), 5273-308. 185. Vizer, S. A.; Yerzhanov, K. B.; Al Quntar, A. A. A.; Dembitsky, V. M. Synthesis of Heterocycles by Carbonylation of Acetylenic Compounds. 2004, 60(26), 5499-538. 186. Crouch, R. D. Selective Monodeprotection of Bis-Silyl Ethers. 2004, 60(28), 5833-71. 187. Henry, G. D. De Novo Synthesis of Substituted Pyridines. 2004, 60(29), 6043-61. 188. Majumdar, K. C.; Basu, P. K.; Mukhopadhyay, P. P. Formation of Five- and Six-Membered Heterocyclic Rings Under Radical Cyclization Conditions. 2004, 60(30), 6239-78. 189. Qiu, X.-L.; Meng, W.-D.; Qing, F.-L. Synthesis of Fluorinated Amino Acids. 2004, 60(32), 6711-45. 190. Grubbs, R. H. Olefin Metathesis. 2004, 60(34), 7117-40. 191. Buncel, E.; Um, I.-H. The a-Effect and Its Modulation by Solvent. 2004, 60(36), 7801-25. Tetrahedron-Assymetry 192. Chelucci, G.; Murineddu, G.; Pinna, G. A. Chiral Pyridine N-Oxides: Useful Ligands for Asymmetric Catalysis. 2004, 15(9), 1373-89. 193. Jerphagnon, T.; Renaud, J.-L.; Bruneau, C. Chiral Monodentate Phosphorus Ligands for Rhodium-Catalyzed Asymmetric Hydrogenation. 2004, 15(14), 2101-11. 194. Dieguez, M.; Pamies, O.; Claver, C. Recent Advances in Rh-Catalyzed Asymmetric Hydroformylation Using Phosphite Ligands. 2004, 15(14), 2113-22. 195. Clark, T.; Landis, C. Recent Developments in Chiral Phospholane Chemistry. 2004, 15(14), 2123-37. 196. Drexler, H.-J.; Zhang, S.; Sun, A.; Spannenberg, A.; Arrieta, A.; Preetz, A.; Heller, D. Cationic Rh-Bisphosphine-Diolefin Complexes as Precatalysts for Enantioselective Catalysis--What Information do Single Crystal Structures Contain Regarding Product Chirality? 2004, 15(14), 2139-50. Topics in Current Chemistry 197. Crepy, K. V. L.; Imamoto, T. New P-Chirogenic Phosphine Ligands and Their Use in Catalytic Asymmetric Reactions. 2003, 229(New Aspects in Phosphorus Chemistry III), 1-40. 198. Taillefer, M.; Cristau, H.-J. New Trends in Ylide Chemistry. 2003, 229(New Aspects in Phosphorus Chemistry III), 41-73. 199. Tanaka, M. Homogeneous Catalysis for H-P Bond Addition Reactions. 2004, 232(New Aspects in Phosphorus Chemistry IV), 25-54. 200. Dutasta, J.-P. New Phosphorylated Hosts for the Design of New Supramolecular Assemblies. 2004, 232(New Aspects in Phosphorus Chemistry IV), 55-91. 201. Michalski, J.; Dabkowski, W. State of the Art. Chemical Synthesis of Biophosphates and Their Analogues via PIII Derivatives. 2004, 232(New Aspects in Phosphorus Chemistry IV), 93-144. 202. Vioux, A.; le Bideau, J.; Mutin, P. H.; Leclercq, D. Hybrid Organic-Inorganic Materials Based on Organophosphorus Derivatives. 2004, 232(New Aspects in Phosphorus Chemistry IV), 145-74. 203. Gudat, D. "Zwitterionic Phospholide Derivatives - New Ambiphilic Ligands". 2004, 232(New Aspects in Phosphorus Chemistry IV), 175-212. Monographs 204. Allen, D. W.; Tebby, J. C. Organophosphorus Chemistry. Vol. 33. Royal Society of Chemistry: Cambridge, U.K., 2003. 205. Astruc, D., Ed. Modern Arene Chemistry. Wiley-VCH Verlag: Weinheim, Germany, 2002. 206. Attanasi, O. A.; Spinelli, D., Eds. Reviews and Accounts on Heterocyclic Chemistry. [In: Targets Heterocycl. Syst., 2002; 6]. Societa Chimica Italiana: Rome, Italy, 2002. 207. Dunkin, I.; Allen, N. S.; Horspool, W. M.; Gilbert, A. Photochemistry. A Review of the Literature Published Between July 2001 and June 2002. Vol. 32. Royal Society of Chemistry: Cambridge, U.K., 2003. 208. Ferrier, R. J. Monosaccharides, Disaccharides and Specific Oligosaccharides. [In: Carbohydr. Chem., 2003; 34]. Royal Society of Chemistry: Cambridge, U.K., 2003. 209. Mingos, D. M. P., Ed. Supramolecular Assembly via Hydrogen Bonds I. [In: Struct. Bonding (Berlin, Ger.), 2004; 108]. Springer-Verlag: Berlin, Germany, 2004. 210. Mingos, D. M. P., Ed. Supramolecular Assembly via Hydrogen Bonds II. [In: Struct. Bonding (Berlin, Ger.); 2004, 111]. Springer-Verlag: Berlin, Germany, 2004. 211. Miyazaki, T., Ed. Atom Tunneling Phenomena in Physics, Chemistry and Biology. [In: Springer Ser. At., Opt., Plasma Phys., 2004; 36]. Springer-Verlag: Berlin, Germany, 2004. 212. O'Neil, I. A. Science of Synthesis, Volume 3, Houben-Weyl Methods of Molecular Transformation; Organometallics: Compounds of Groups 12 and 11 (Zn, Cd, Hg, Cu, Ag, Au). Georg Thieme Verlag: Stuttgart, Germany, 2004. 213. Thomas, E. J. Hetarenes and Related Ring Systems Six-Membered Hetarenes with One Chalcogen. [In: Sci. Synth., 2003; 14]. Georg Thieme Verlag: Stuttgart, Germany, 2003. 214. Ward, M. D., Ed. Comprehensive Coordination Chemistry II, Volume 9: Applications of Coordination Chemistry. Elsevier Ltd.: Oxford, U.K., 2004. Index Acetoacetic esters, aldol condensation, 111 Acetylenes, silylation, 24 Acetylenic compounds, carbonylation, 185 Acid-base catalysis, asymmetric direct aldol reaction, 12 Adenosine A3 receptor antagonists, 127 agonists, 126 Alcohols, oxidation, solvent-free, 120 Aldehydes, allylboronate addition, 181 a-aminoxylation, 37 preparation, solvent-free, 120 Aldol reaction, titanium BINOL catalyst, 111 intermolecular, organocatalysis, 11 Alkenes, asymmetric hydrogenation, with Rh, 18 functionalization, 60 hydroamination, 21 oxidative cyclization, with Pd, 42 reduction with NiCl2-Li-arene, 55 regioselective functionalization, 41 substitution with alkylarylsulfanyltetrazoles, 162 Alkenylfuranose, cycloaddition, 97 Alkyl anthracenylmethyl cinchona alkaloids, 6 Alkylzinc reagent, selective ring opening allylic substitution, 149 Alkynes, regioselective functionalization, 41 Allenes, silylation, 24 Allenylfuranose cycloaddition, 97 Allosteric supramolecules, catalysts, 47 receptors, 47 Allylboronates, camphor-diol, 181 Allylic substitution, Pd catalyzed, 76 Allylsilanes, preparation, 24 Alpha effect, solvent effect, 191 Aluminum, reducing agent, 112 Amines, kinetic resolution, 9 synthesis, 175 Amino acids, catalysts, 11 dialkyl, 175 fluorinated, 189 immobilized, ion exchange chromatography, 157 immobilized, metal binding, 157 a-, via chiral phase transfer catalyst, 5 Aminobenzylnaphthols, 121 Aminopyrimidines, carbonyl condensation, 160 Aminotetradeoxynonulosonic acid, 26 Analgesics, 68 Anatoxin-a, 124 Anti HIV agents, conduritols, 115 Anticancer agents, 176 Antidepressive agents, 68 Antimicrobial agents, 68 Antimitotic agents, colchicines, 39 Antitumor agents, organotin, 144 thionucleosides, 93 Antiviral agents, thionucleoside, 93 Aporphinoid alkaloids, 147 Arenes, book, 205 dihapto coordinated, 90 hydroxylated, oxidative activation, 94 Aromatic heterocycles, dihapto coordinated, 90 Aromatics, polycyclic, synthesis, 96 Arsaalkene, fluorinated, 135 Arylboronic acid, aryl chloride coupling, 35 Arylcyclopropanes, heterocycle synthesis, 67 Arylphosphonates, 99 Atom tunneling, book, 211 Azabicycloalkane amino acids, 177 Azabutadiene iron complex, 142 Azacycles, solid phase synthesis, 175 Azoalkanes, bicyclic, denitrogenation, 143 Bellus Claisen rearrangement, 43 Benzannulated pyridines, organometallic complexes, 30 Benzothiopene desulfurization, 84 Benzyl amines, deamination, 179 Betaines, heterocyclic, mesomericm, 100 Betti bases, chiral ligands, 121 Biginelli cyclocondensation libraries, 159 Bioconjugates, preparation, chemoselective ligation, 38 Biophosphates, synthesis, 201 Boron, organometallic complex, 28 Butadienes, fluorinated, 137 Calixarene derivatives, conformations, 79 Calystegines, 145 Carbenes, nucleophilic, asymmetric catalysis, 8 Carbocycles, from quinones, 173 preparation, intramolecular Heck reaction, 106 unsaturated, seven membered, 173 from catechols, 173 Carbohydrates, microwave chemistry, 98, 172 Carbonates, cyclic, from carbon dioxide, 64 Carbon-carbon double bond, 170 Carbon-transition metal double bond, 81 Carbon-transition metal triple bond, 81 Carbonyl protecting group, deprotection, 151 Carbonylation, oxidative, with Pd, 110 Carboranes, icosahedral, 83 Cardiovascular agents, 68 Catalysis, metal, single pot, 44 Catalysts, multiple, one-pot, 57 Catenanes, multi-, from calixarenes, 166 Cavitands, phosphorylated, 200 C-C bond activation, Rh chelation, 156 C-C bond formation, from C=N bond, 175 via capture hydrogenation intermediate, 20 C-C bonds, from chiral, C-transition metal complexes, 62 radical mediated, 71 C-H bond activation, Rh chelation, 156 Chalcogens, six-membered rings, book, 213 Chiral catalyst libraries, 63 Chlorosulfonyl isocyanate, b-lactam synthesis, 97 Cinchona alkaloids, asymmetric catalysis, 17 chiral phase transfer catalyst, 5 phase transfer catalyst, 6 Co-catalyst systems, 57 Colchicine total synthesis, 39 Combinatorial asymmetric transition metal catalysis, 73 Combinatorial chemistry, chiral catalysts, 63 functional group detection, 130 triazene linkers, 23 Conduritol,115 Coordination chemistry, book, 214 Cyclic ADP-ribose analog, 92 Cyclitols, 115 Cycloalkanedione, heterocycle synthesis, 102 Cyclodextrins, capillary electrophoresis, NMR, 59 enantioselective recognition, 59 molecular modeling, 59 oligomers, 116 Cyclohexenes, epoxidation, 4 Cycloproparadicicol anticancer agent, 176 Cyclopropylamine, via Ti catalyst, 140 Decamethylsilicocene reaction, proton transfer reagent, 169 Deprotection, carbonyl group, 151 Diacylbenzenes, in synthesis, 152 Diazino-fused ring systems, 174 Dibismuthines, 87 Dieckmann cyclization of glycolyl acetoacetate, 154 Dienes, silylation, 24 Difluoropropadienes, 137 Dihydropyridine, non-biomimetic reactions, 103 Dihydropyrimidines, solid phase synthesis, 159 Diketones, cyclic, heterocycle synthesis, 102 Dimethylaminopyridine, planar chiral, 9 Diols, monophosphorylation, 179 Disaccharide mimetics, C-linked, 150 Distibines, 87 Enamine catalysis, carbonyl reactions, 10 Enamine organocatalysis, 13 Enediyne, Bergman cyclization, 77 Ephedra alkaloids, in synthesis, 101 Ephedra heterocycles, chiral preparation, 101 Epibatidine analogs, 124 Epoxidation, asymmetric, 16 Epoxides, from sulfur ylides, 16 Erythrinane alkaloids, 147 Ferrocenes, unsymmetric ligands, 58 Ferrocenyl oligomers, 82 Fluoride ion donors, 138 Fluorination, electrochemical, 132 Fluorocarbon oxy radicals, 139 Fullerenes, C50, chlorinated, 163 fluorinated, 133 Fulvalene bridge, 89 Glycine imines, alkylation, 6 Glycopolymers, bacterial, 26 Glycosyl phosphates, oligosaccharide synthesis, 25 Heck reaction, intramolecular, 106 Hemicryptophanes, phosphorylated, 200 Hetarenes, book, 213 Heteroannulation, Pd catalyst, 117 Heterobinuclear organometallic complex, 89 Heterocumulenes, 108 Heterocycles, benzoannelated, N-containing, 23 biologically active, preparation, 105 ephedra, 101 five-membered, radical cyclization, 188 five-membered, via Pd catalysis, 117 from catechols, 173 from cyclocarbonylation of acetylenes, 185 from pyrrole oximes, 68 from quinones, 173 N-containing, 108 N-containing, from arylcyclopropane, 67 O-containing, from arylcyclopropane, 67 preparation, intramolecular Heck reaction, 106 seven membered, 173 six-membered, radical cyclization, 188 six-membered, via Pd catalysis, 117 via intramolecular aryl radical reactions, 105 Heterocyclic carbenes, nucleophilic, 88 Suzuki Miyaura coupling, 35 Heterocyclic chemistry, book, 206 Heterocycloquinolines, 27 Heterophospholes, cycloaddition, 128 Histamines, fluorinated, 134 Host-guest chemistry, phosphorylated host, 200 Houben Weyl molecular transformation, book, 212 Hydroamination of alkenes, 21 Hydroformylation, asymmetric, phosphite ligands, 194 Hydrogenation, asymmetric, Rh, P ligands, 193 triphase, microchannel, 165 Hydroquinones, deprotonation, 84 Hydrosilylation, Ru catalyst, 36 Hydroxybenzyl acetate, 161 Hydroxyfuranones, synthesis, 154 Hydroxypyrimidines, carbonyl condensation, 160 Imidazoles, fluorinated, 134 Iminodihydrofuranones, 69 Iminophosphoranes, aza Wittig reaction, 108 building blocks, 108 Indium compounds, in synthesis, 123 Indole alkaloids, 146 Indoles, fluorinated, 134 Iodine electrophiles, stereoselective, 60 Iridoids, natural product synthesis, 155 Isopolyhalomethanes, 104 Isoprostanes, natural product synthesis, 155 Isoquinoline alkaloids, 147 asymmetric synthesis, 50 Isoxazoles, flash vacuum pyrolysis, 114 hydroxy-, using Meldrum acid, 178 Jasmonoids, natural product synthesis, 155 Ketal cleavage, phenyl dichlorophosphate, 179 Ketone preparation, phenyl dichlorophosphate, 179 solvent free, 120 Ketones, catalytic ionic hydrogenation, 61 chiral, for epoxidation of olefins, 3 enantioselective Baeyer Villiger oxidation, 113 halogenation, 179 a-aminoxylation, 37 Lactams, b-, asymmetric synthesis, 14 using Meldrum's acid, 178 synthesis, 9, 97 synthesis, Kinugasa reaction, 34 via phenyl dichlorophosphate, 179 Lactonization, halo-, 184 seleno, 184 Lewis base catalysts, 9 Ligands, all carbon, 33 Meldrum acid, 178 Metallabenzynes, 1 Metallacarboranes, cobalt, 85 Metallacycles, five-membered, 45 Metallocenes, Mn tricarbonyl, 84 Metallocyclopentynes, 45 Metathesis catalyst, supported, 148 Methane dissociation, gas-surface reactions, 164 Microwaves, in synthesis, 109 Mitsunobu reaction, separations, 66 Molecular reactors, 65 Monosaccharides, book, 208 C-substituted, 150 Naphthalene, bimetallic complexes, 84 Mn tricarbonyl transfer agents, 84 Naphthylisoquinoline alkaloids, 147 Natural product heterocycles, preparation, 105 Natural products, polycyclic, from acyclic precursors, 74 Natural products, synthesis, allylic substitution, 155 Natural products, synthesis with SmI2, 51 Nickel catalyst, reductive coupling, 46 reductive cyclization, 46 Nickel dichloride lithium arene, 55 Nicotine alkaloids, 124 Nicotinic acetylcholine receptor ligands, 124 Nitroso compounds, 49 Nortropane alkaloids, 145 Norzoanthamine, total synthesis, 167 Nucleic acid bases, electron binding, 80 Nucleophilic heterocyclic carbenes, 88 Nucleosides, C-, preparation, 182 Olefin epoxidation, with inorganic peroxide, 19 Olefin ligands, bidentate, chiral, 40 Olefin metathesis, Ru catalyst, 190 Olefins, asymmetric epoxidation with chiral ketones, 4 epoxidation, with chiral ketones, 3 Oligosaccharides, book, 208 solid phase synthesis, 25 synthesis, 25 Organocatalysis, asymmetric, 2, 11 Organofluorine compounds, via iodine fluorides, 131 Organogermanes, cross coupling, 122 Organolanthanide catalysis, 21 Organometallics, chiral, C-transition metal, 62 double bonds, 81 metal clusters, 91 unsaturated hydrocarbon bridges, 89 Organophosphorus compounds, book, 204 preparation, 199 organic/inorganic hybrids, 202 Organosilanes, cross coupling, 122 Organosilicon compounds, 169 direct synthesis, 32 hydrazide-based, 31 Organostannane compounds, 141 Organotin compounds, 141, 144 Osmabenzynes, 1 Oxacycles, solid phase synthesis, 175 Oxanorbornenes, allylic substitution, 149 reaction with dialkylzinc, 149 Oxazoline chiral ligands, asymmetric synthesis, 53 Oxidative carbonylation, Pd catalyst, 110 Oxime ethers, alkylation, 175 preparation, 68 Oxoammonium oxidizing agents, 153 Palladium ligands, stereoselective synthesis, 52 Palladium oxidase catalyst, 42 Peptide catalysts, asymmetric synthesis, 15 Peptides, beta-sheet, 56 immobilized, metal binding, 157 molecular scaffolds, 56 solid phase synthesis, analysis, 95 Peptidomimetics, 177 Perfluorinated organic compounds, 132 Perfluoroorganosilver compounds, 136 Pfitzinger reaction, 70 Phenols, sterically hindered, 161 Phenyl dichlorophosphate, 179 Phenyl ethenyl ferrocenyl oligomers, 82 Phenylethylamines, 147 Phenylsilane, alkylation, 36 Phosphaalkenes, fluorinated, 135 Phosphine ligand, P-chirogenic, 197 Phosphine ligands, Suzuki-Miyaura coupling, 35 Phosphitylating reagent, 201 Phospho Fries rearrangement, anionic, 99 Phospholane ligand, chiral, 195 Phospholanes, asymmetric catalysis, 195 Phospholide zwitterion ligands, 203 Phosphoroamidites, activation, 201 Phosphorofluoridites, 201 Phosphorus hydrogen bond additions, 199 Phosphorus ligands, asymmetric hydrogenation, 193 chiral, 73 Phosphorus ylide chemistry, 198 Phosphorus, organometallic complex, 28 Photochemistry, book, 207 Phthalaldehydes, ortho-, with nucleophiles, 48 Piperazinones, bridged, stereoselective preparation, 72 Plant growth regulators, 68 Polycyclic aromatic hydrocarbons, 96 Polysaccharide, bacterial, biosynthesis, 26 Propadienes, fluorinated, 137 Pyrazoles, flash vacuum pyrolysis, 114 Pyridazino fused rings, preparation, 174 Pyridine oxides, chiral, 192 Pyridines, organometallic complexes, 30 subsituted, synthesis, 187 Pyridinium alkaloids, betainic, 100 Pyridooxazines, 29 Pyridopyrimidines, 29 Pyridothiazines, 29 Pyrones, substituted, preparation, 178 Pyrrole aldoximes, 68 Pyrrole ketoximes, 68 Pyrrole oximes, 68 Quaternary ammonium fluorides, chiral catalysts, 7 Quaternary ammonium salts, chiral catalysts, 6 Quinoid supramolecules, from hydroquinones, 84 Quinoline alkaloids, preparation, 105 Quinoline carboxylic acid preparation, 70 Quinolones, using Meldrum acid, 178 Quinoxalines, dehydration, cyclization, 179 Radicicol anticancer agent, 176 Reducing agents, NiCl2-Li-arene, 55 Rhodium bisphosphine diolefin enantioselective catalysts, 196 Samarium iodide, in cyclization, 51 Selenabenzenes, 107 Selenanaphthalene, 107 Selenium carborane ligands, 86 Selenocarbonyls, fluorinated, 135 Serotonin, fluorinated, 134 Silicon, organometallic complex, 28 Silyl ethers, monodeprotection, 186 Silyl ketene acetals, acylation, 9 Silylcupration, 24 Silylenes, 168 Silylium ions, 168 Silyliumylidene cation, 169 Silyliumylidenes, 168 Sisaccharides, book, 208 Solid phase synthesis, colorimetric, 130 functional group detection, 130 Solvents, fluorous phase, 125 ionic liquids, 125 supercritical carbon dioxide, 125 Spacers, conformation,biologically active molecules, 158 Sparteine synthesis, 75 Staudinger ligation, 38 Steroid derivatives, combinatorial library, 129 Steroid glycosylation, 183 Styrenes, silylation, 24 Sulfanylpyrimidines, carbonyl condensation, 160 Sulfanyltetrazoles, alkylaryl-, 162 Sulfenyl chloride chemistry, 170 Sulfone radicals, C-C bond formation, 71 Sulfur carborane ligands, 86 Supramolecules, H bond, book, 209-10 P-stabilized, 200 Tellurium carborane ligands, 86 Tetrafluoroallenes, 137 Tetrafluorobutatrienes, 137 Tetrahydropyridine, alkaloid synthesis, 119 Tetramethylcyclobutadiene cobalt complex, 85 Tetramethylpiperidine oxoammonium salt, oxidants, 153 Tetraorganostannane halides, 141 Tetronic acids, synthesis, 154 Thiacalixarenes, functionalization, 78 Thiamine, organocatalysis, 8 Thioesters, via phenyl dichlorophosphate, 179 Titancyclopropanes, 140 Toluenesulfonylmethyl isocyanide synthon, 171 Transesterification acylation reaction, 180 Triazene linker, solid phase synthesis, 23 Triazenes, arene amine linkers, 23 Triphenylenes, preparation, 54 Triphenylmethanesulfenyl chloride, 170 Vicinal tricarbonyls, cyano analog, 22 Vinyl epoxides, allylic substitution, 149 reaction with dialkylzinc, 149 Vinylaziridines, allylic substitution, 149 reaction with dialkylzinc, 149 Vinylsilanes, preaparation, 24 Welwistatin synthesis, 118 Ylide chemistry, 198 Zwitterionic phospholide ligands, 203