Decarboxylative benzylation and arylation of nitriles

Fe-catalysed oxidative C–H functionalization/C–S bond formation

Haibo Wang, Lu Wang, Jinsai Shang, Xing Li, Haoyuan Wang, Jie Gui and Aiwen Lei 

Chem. Commun., 2012, 48, 76-78

DOI: 10.1039/C1CC16184A

Dehydrogenation processes via C–H activation within alkylphosphines

Mary Grellier and Sylviane Sabo-Etienne 

Chem. Commun., 2012, 48, 34-42

DOI: 10.1039/C1CC14676A

Transition Metal Catalyzed Denitrogenative Transannulation: Converting Triazoles into Other Heterocyclic Systems

Converting Triazoles into Other Heterocyclic Systems

Simple and Sustainable Copper–O2 Chemistry towards High-Value Products

Methyl 2-Furoate: An Alternative Reagent to Furan for Palladium-Catalysed Direct Arylation

Mechanistic Origin of Ligand-Controlled Regioselectivity in Pd-Catalyzed C[BOND]H Activation/Arylation of Thiophenes

Mechanistic Analysis of Iridium(III) Catalyzed Direct C[BOND]H Arylations: A DFT Study

doi/10.1002/chem.201101532

Rhodium(III)-Catalyzed Synthesis of Pyridines from α,β-Unsaturated Ketoximes and Internal Alkynes

Synthesis of Angiotensin II Receptor Blockers by Means of a Catalytic System for C–H Activation

Metal-Free Intermolecular Oxidative C–N Bond Formation via Tandem C–H and N–H Bond Functionalization

Brenton DeBoef, 2011, JACS DOI: 10.1021/ja2087085

Pd(II)-Catalyzed Enantioselective C–H Activation of Cyclopropanes

Jin-Quan Yu, 2011, JACS DOI: 10.1021/ja207607s

Reversed-Polarity Synthesis of Diaryl Ketones via Palladium-Catalyzed Cross-Coupling of Acylsilanes

DOI: 10.1021/ja2064318

One-Pot Synthesis of Isoquinolinium Salts by Rhodium-Catalyzed C[BOND]H Bond Activation: Application to the Total Synthesis of Oxychelerythrine

DOI: 10.1002/anie.201105755

Palladium-Catalyzed Decarboxylative C[BOND]H Bond Arylation of Thiophenes

Silanol as a Removable Directing Group for the PdII-Catalyzed Direct Olefination of Arenes

DOI: 10.1002/chem.201103171

sp3-sp2 C-C Bond Formation via Brønsted Acid Trifluoromethanesulfonic Acid-Catalyzed Direct Coupling Reaction of Alcohols and Alkenes

Aryl Diazonium versus Iodonium Salts: Preparation, Applications and Mechanisms for the Suzuki–Miyaura Cross-Coupling Reaction

DOI: 10.1002/adsc.201100531

Ruthenium-Catalyzed Regioselective Cyclization of Aromatic Ketones with Alkynes: An Efficient Route to Indenols and Benzofulvenes

Iron-Catalyzed Direct Alkenylation of 2-Substituted Azaarenes with N-Sulfonyl Aldimines via C–H Bond Activation

Org. Lett., 2011, 13 (10), pp 2580–2583

Light-Harvesting Hybrid Hydrogels: Energy-Transfer-Induced Amplified Fluorescence in Noncovalently Assembled Chromophore–Organoclay Composites

The noncovalent self-assembly of chromophores in an organoclay template results in the formation of fluorescent hybrid hydrogels and films. These clay–dye hybrids act as novel supramolecular scaffolds for light-harvesting as the aminoclay (AC) templates the spatial organization of donor and acceptor molecules to promote Förster resonant energy transfer (see picture; CS=coronene salt, PS=perylene salt).

This artle also highlited in NATURE.

http://www.nature.com/nindia/2011/110228/full/nindia.2011.30.html

Participation of Carbonyl Oxygen in Carbon–Carboxylate Bond-Forming Reductive Elimination from Palladium

Melanie S. Sanford, Organometallics, DOI: 10.1021/om200677y

Ruthenium-Catalyzed C–H/N–O Bond Functionalization: Green Isoquinolone Syntheses in Water

Lutz Ackermann, OL, 2011, DOI: 10.1021/ol202861k

Copper-Mediated Chelation-Assisted Ortho Nitration of (Hetero)arenes

DOI: 10.1021/ol2028288

Copper-Catalyzed, One-Pot, Three-Component Synthesis of Benzimidazoles by Condensation and C–N Bond Formation

DOI: 10.1021/jo2019416

Borylation and Silylation of C–H Bonds: A Platform for Diverse C–H Bond Functionalizations

Direct Functionalization of M–C (M = PtII, PdII) Bonds Using Environmentally Benign Oxidants, O2 and H2O2

Andrei N. Vedernikov, Acc. Chem. Res., 2011, DOI: 10.1021/ar200191k

Ligand-Promoted C3-Selective Arylation of Pyridines with Pd Catalysts: Gram-Scale Synthesis of (±)-Preclamol

Jin-Quan Yu, JACS, 2011, DOI: 10.1021/ja209510q

Nickel-Catalyzed Heck-Type Reactions of Benzyl Chlorides and Simple Olefins

Timothy F. Jamison, JACS, 2011, DOI: 10.1021/ja209235d

Ruthenium-Catalyzed Meta Sulfonation of 2-Phenylpyridines

Christopher G. Frost, JACS, 2011, DOI: 10.1021/ja208286b

Nickel-Catalyzed Suzuki–Miyaura Reaction of Aryl Fluorides

Naoto Chatani, JACS, 2011, DOI: 10.1021/ja207759e

Synthesis of Dragmacidin D via Direct C–H Couplings

Junichiro Yamaguchi and Kenichiro Itami, JACS, 2011, DOI: 10.1021/ja209945x

Assymmetric C-H activation: Enantioselective Rhodium(I)-Catalyzed [3+2] Annulations of Aromatic Ketimines Induced by Directed C[BOND]H Activations

1. Prof. Dr. Nicolai Cramer, 2011, ACIE, 

DOI: 10.1002/anie.201105766

Palladium-Catalyzed Regioselective γ-Mono- and Diarylation of Acrylamide Derivatives with Aryl Halides

DOI: 10.1002/adsc.201100373

Palladium(II)-Catalyzed Direct ortho-C[BOND]H Acylation of Anilides by Oxidative Cross-Coupling with Aldehydes using tert-Butyl Hydroperoxide as Oxidant

DOI: 10.1002/adsc.201100472

Metal-Free C–H Cross-Coupling toward Oxygenated Naphthalene-Benzene Linked Biaryls

DOI: 10.1021/ol202632h

Ruthenium-Catalyzed Ortho-Alkenylation of Aromatic Ketones with Alkenes by C–H Bond Activation

DOI: 10.1021/ol202580e

Palladium-Catalyzed C–C Bond Formation of Arylhydrazines with Olefins via Carbon–Nitrogen Bond Cleavage

DOI: 10.1021/ol202862t

Palladium-Catalyzed Direct Olefination of Urea Derivatives with n-Butyl Acrylate by C–H Bond Activation under Mild Reaction Conditions

DOI: 10.1021/ol202738j

Bimetallic Redox Synergy in Oxidative Palladium Catalysis

Tobias Ritter. 2011, JACS, Acc. Chem. Res, DOI: 10.1021/ar2001974

Room-Temperature C–H Arylation: Merger of Pd-Catalyzed C–H Functionalization and Visible-Light Photocatalysis

Melanie S. Sanford, JACS, 2011, DOI: 10.1021/ja208068w

Stains for TLC Identification

        Once a TLC has been developed, it is frequently necessary to aid in the visualization of the components of a reaction mixture. This is true primarily because most organic compounds are colorless. Frequently, the organic compounds of interest contain a chromophore which may be visualized by employing either a short or a long wave UV lamp. These lamps may be found as part of a standard organic chemistry research or teaching lab. Typical examples of functional groups which may be visualized through this method are aromatic groups, a,b-unsaturated carbonyls, and any other compounds containing extensively p-conjugated systems. While exposing these TLC plates to UV light, you will notice that the silica gel will fluoresce, while any organic molecule which absorbs UV light will appear as a dark blue spot. Circling these spots gently with a dull pencil will permit an initial method for visualization. Fortunately, there are a number of permanent or semi-permanent methods for visualization which will not only allow one to see these compounds but also provide a method for determining what functional groups are contained within the molecule. This method is referred to as staining the TLC plate, and experience will allow you to determine what functional groups will appear as what color upon visualization. Following is a listing of the most commonly employed stains, the kind of compounds for which they're usually employed, and a typical recipe.

A Note on TLC Plates     Although it should be obvious, be sure that the kind of TLC plate you are using is compatible with the stain or the conditions for its development.  For instance, the inexpensive plates using a plastic polymer backing cannot be used for stains requiring heat for development.  Glass backing is fine for this, but the silica gel is typically not tightly bonded to the glass, and tends to be inadvertantly scraped off very easily; thus, these are not suitable for storage following development.  In our group, we use aluminum-backed plates, which are less expensive than glass, are heat-impervious, the silica gel is very tightly bound to the backing, and are so thin that, if desired, a particularly spectacular plate can be taped into your lab notebook. The Stain List Iodine The staining of a TLC plate with iodine vapor is among the oldest methods for the visualization of organic compounds. It is based upon the observation that iodine has a high affinity for both unsaturated and aromatic compounds. Recipe A chamber may be assembled as follows: To 100 mL wide mouth jar (with cap) is added a piece of filter paper and few crystals of iodine. Iodine has a high vapor pressure for a solid and the chamber will rapidly become saturated with iodine vapor. Insert your TLC plate and allow it to remain within the chamber until it develops a light brown color over the entire plate. Commonly, if your compound has an affinity for iodine, it will appear as a dark brown spot on a lighter brown background. Carefully remove the TLC plate at this point and gently circle the spots with a dull pencil. The iodine will not remain on the TLC plate for long periods of time so circling these spots is necessary if one wishes to refer to these TLC's at a later date. Ultraviolet Light Good for visualizing any compounds which are UV-active, particularly those with extended conjugation, aromatic rings, etc.  Spot(s) must be lightly traced with a pencil while visible, since when the UV light is removed, the spots disappear. Ceric Ammonium Sulfate       Specifically developed for vinca alkaloids (aspidospermas). Recipe Prepare a 1% solution of of cerium (IV) ammonium sulfate in 50% phosphoric acid. Cerium Sulfate       General stain, particularly effective for alkaloids. Recipe Prepare an aqueous solution of 10% cerium (IV) sulfate and 15% sulfuric acid. Ferric Chloride      Excellent for phenols. Recipe Prepare a solution of 1% ferric (III) chloride in 50% aqueous methanol. Morin Hydrate       General stain (morin is a hydroxy flavone), is fluorescently active. Recipe Prepare a 0.1% solution of morin hydrate (by weight) in methanol. Ninhydrin       Excellent for amino acids Recipe Dissolve 1.5g ninhydrin in 100mL of n-butanol and then add 3.0mL acetic acid. Dinitrophenylhydrazine (DNP)      Developed mainly for aldehydes and ketones; forms the corresponding hydrazones, which are usually yellow to orange and thus easily visualized. Recipe Dissolve 12g of 2,4-dinitrophenylhydrazine, 60mL of conc. sulfuric acid, and 80mL of water in 200mL of 95% ethanol. Vanillin      Very good general stain, giving a range of colors for different spots. Recipe Prepare a solution of 15g vanillin in 250mL ethanol and 2.5mL conc. sulfuric acid. Potassium Permanganate      This particular stain is excellent for functional groups which are sensitive to oxidation. Alkenes and alkynes will appear readily on a TLC plate following immersion into the stain and will appear as a bright yellow spot on a bright purple background. Alcohols, amines, sulfides, mercaptans and other oxidizable functional groups may also be visualized, however it will be necessary to gently heat the TLC plate following immersion into the stain. These spots will appear as either yellow or light brown on a light purple or pink background. Again it would be advantageous to circle such spots following visualization as eventually the TLC will take on a light brown color upon standing for prolonged periods of time. Recipe Dissolve 1.5g of KMnO4, 10g K2CO3, and 1.25mL 10% NaOH in 200mL water.   A typical lifetime for this stain is approximately 3 months. Bromocresol Green Stain       This particular stain is excellent for functional groups whose pKa is approximately 5.0 and lower. Thus, this stain provides an excellent means of selectively visualizing carboxylic acids. These will appear as bright yellow spots on either a dark or light blue background and typically, it is not necessary to heat the TLC plate following immersion. This TLC visualization method has a fairly long lifetime (usually weeks) thus, it is not often necessary to circle such spots following activation by staining. Recipe To 100 ml of absolute ethanol is added 0.04 g of bromocresol green. Then a 0.1 M solution of aqueous NaOH is added dropwise until a blue color just appears in solution (the solution should be colorless prior to addition). Ideally, these stains may be stored in 100 mL wide mouth jars. The lifetime of such a solution typically depends upon solvent evaporation. Thus, it would be advantageous to tightly seal such jars in-between uses. Cerium Molybdate Stain (Hanessian's Stain)       This stain is a highly sensitive, multipurpose (multifunctional group stain). One word of caution, very minor constituents may appear as significant impurities by employing this stain. To ensure accurate results when employing this stain, it is necessary to heat the treated TLC plate vigorously (a heat gun works well). Thus, this may not be a stain to employ if your sample is somewhat volatile. The TLC plate itself will appear as either light blue or light green upon treatment, while the color of the spots may vary (although they usually appear as a dark blue spot). Typically, functional groups will not be distinguishable based upon the color of their spots; however, it would be worth while to make a list of potential colors of various functional groups as you experience variations in colors. This may permit future correlations which may prove beneficial when performing similar chemistry on related substrates. Recipe To 235 mL of distilled water was added 12 g of ammonium molybdate, 0.5 g of ceric ammonium molybdate, and 15 mL of concentrated sulfuric acid. Storage is possible in a 250 mL wide mouth jar. This stain has a long shelf-life so long as solvent evaporation is limited. It may also prove worth while to surround the jar with aluminum foil as the stain may be somewhat photo-sensitive and exposure to direct light may shorten the shelf-life of this reagent. It is worth while to also mention that it would be beneficial to circle the observed spots with a dull pencil following heating as this stain will eventually fade on the TLC plate after a few days. p-Anisaldehyde Stain #1       This stain is an excellent multipurpose visualization method for examining TLC plates. It is sensitive to most functional groups, especially those which are strongly and weakly nucleophilic. It tends to be insensitive to alkenes, alkynes, and aromatic compounds unless other functional groups are present in the molecules which are being analyzed. It tends to stain the TLC plate itself, upon mild heating, to a light pink color, while other functional groups tend to vary with respect to coloration. It is recommended that a record is kept of which functional group stains which color for future reference, although these types of comparisons may be misleading when attempting to ascertain which functional groups are present in a molecule (especially in complex molecules). The shelf-life of this stain tends to be quite long except when exposed to direct light or solvent is allowed to evaporate. It is recommended that the stain be stored in a 100 mL wide mouth jar wrapped with aluminum foil to ensure a long life time. Recipe To 135 mL of absolute ethanol was added 5 mL of concentrated sulfuric acid, 1.5 mL of glacial acetic acid and 3.7 mL of p-anisaldehyde. The solution is then stirred vigorously to ensure homogeneity. The resulting staining solution is ideally stored in a 100 mL wide mouth jar covered with aluminum foil. p-Anisaldehyde Stain #2       A more specialized stain than #1 (above), used for terpenes, cineoles, withanolides, acronycine, etc.  As above, heating with a heat gun must be employed to effect visualization. Recipe Prepare solution as follows: anisaldehyde:HClO4:acetone:water (1:10:20:80) Phosphomolybdic Acid (PMA) Stain       Phosphomolybdic acid stain is a good "universal" stain which is fairly sensitive to low concentrated solutions. It will stain most functional groups, however it does not distinguish between different functional groups based upon the coloration of the spots on the TLC plate. Most often, TLC's treated with this stain will appear as a light green color, while compounds of interest will appear as much darker green spots. It is necessary to heat TLC plates treated with this solution in order to activate the stain for visualization. The shelf life of these solutions are typically quite long, provided solvent evaporation is kept to a minimum. Recipe Dissolve 10 g of phosphomolybdic acid in 100 mL of absolute ethanol. Occasionally, if you find it necessary to develop or investigate other staining techniques, the following references may be helpful: Handbook of Thin-Layer Chromatography J. Sherman and B. Fried, Eds., Marcel Dekker, New York, NY, 1991. Thin-Layer Chromatography 2nd ed. E. Stahl, Springer-Verlag, New York, NY, 1969. Thin-Layer Chromatography Reagents and Detection Methods, Vol. 1a: Physical and Chemical Detection Methods: Fundamentals, Reagents I H. H. Jork, W. Funk, W. Fischer, and H. Wimmer, VHC, Weinheim, Germany, 1990. Thin-Layer Chromatography: Techniques of Chemistry, Vol. XIV, 2nd ed. J. G. Kirchner and E. S. Perry, Eds., John Wiley and Sons, 1978.

Boronic Acids

Wiley: Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials, By Dennis Hall, Second, Completely Revised Edition, 2 Volume Set:

Table of Content:

Contents to Volume 1

Foreword V

Contents to Volume 2 XIII

Preface XV

List of Contributors XIX

1 Structure, Properties, and Preparation of Boronic Acid Derivatives: Overview of Their Reactions and Applications 1 Dennis G. Hall

1.1 Introduction and Historical Background 1

1.2 Structure and Properties of Boronic Acid Derivatives 2

1.3 Preparation of Boronic Acids and Their Esters 31

1.4 Isolation and Characterization 73

1.5 Overview of the Reactions of Boronic Acid Derivatives 78

1.6 Overview of Other Applications of Boronic Acid Derivatives 97

References 109

2 Metal-Catalyzed Borylation of C–H and C–Halogen Bonds of Alkanes, Alkenes, and Arenes for the Synthesis of Boronic Esters 135 Tatsuo Ishiyama and Norio Miyaura

2.1 Introduction 135

2.2 Borylation of Halides and Triflates via Coupling of H–B and B–B Compounds 137

2.3 Borylation via C–H Activation 148

2.4 Catalytic Cycle 159

2.5 Summary 161

References 161

3 Transition Metal-Catalyzed Element-Boryl Additions to Unsaturated Organic Compounds 171 Michinori Suginome and Toshimichi Ohmura

3.1 Introduction 171

3.2 Diboration 172

3.3 Silaboration 185

3.4 Carboboration 202

3.5 Miscellaneous Element-Boryl Additions 207

3.6 Conclusion 208

References 208

4 The Contemporary Suzuki–Miyaura Reaction 213 Cory Valente and Michael G. Organ

4.1 Introduction 213

4.2 Developments Made in the Coupling of Nontrivial Substrates 215

4.3 Asymmetric Suzuki–Miyaura Cross-Couplings 241

4.4 Iterative Suzuki–Miyaura Cross-Couplings 248

4.5 Conclusions and Future Outlook 256

References 257

5 Rhodium- and Palladium-Catalyzed Asymmetric Conjugate Additions of Organoboronic Acids 263 Guillaume Berthon-Gelloz and Tamio Hayashi

5.1 Introduction 263

5.2 Rh-Catalyzed Enantioselective Conjugate Addition of Organoboron Reagents 263

5.3 Pd-Catalyzed Enantioselective Conjugate Addition of Organoboron Reagents 299

5.4 Conclusions 306

References 307

6 Recent Advances in Chan–Lam Coupling Reaction: Copper-Promoted C–Heteroatom Bond Cross-Coupling Reactions with Boronic Acids and Derivatives 315 Jennifer X. Qiao and Patrick Y.S. Lam

6.1 General Introduction 315

6.2 C–O Cross-Coupling with Arylboronic Acids 316

6.3 C–N Cross-Coupling with Arylboronic Acids 321

6.4 Substrate Selectivity and Reactivity in Chan–Lam Cross-Coupling Reaction 335

6.5 C–N and C–O Cross-Coupling with Alkenylboronic Acids 336

6.6 C–N and C–O Cross-Coupling with Boronic Acid Derivatives 338

6.7 C–S and C–Se/C–Te Cross-Coupling 346

6.8 Mechanistic Considerations 349

6.9 Other Organometalloids 354

6.10 Conclusion 355

6.11 Note Added in Proof 355

References 357

Contents to Volume 2

7 Transition Metal-Catalyzed Desulfitative Coupling of Thioorganic Compounds with Boronic Acids 363 Ethel C. Garnier-Amblard and Lanny S. Liebeskind

7.1 General Introduction 363

7.2 Boronic Acid-Thioorganic C–S Desulfitative Cross-Couplings Using Catalytic Nickel or Palladium 364

7.3 Thioorganic C–S Desulfitative Cross-Couplings Using Only Catalytic Copper 380

7.4 Miscellaneous 387

7.5 Conclusions 388

References 388

8 Catalytic Additions of Allylic Boronates to Carbonyl and Imine Derivatives 393 Tim G. Elford and Dennis G. Hall

8.1 Introduction 393

8.2 Additions to Aldehydes 395

8.3 Additions to Ketones 412

8.4 Additions to Imine Derivatives 418

8.5 Conclusions 422

References 423

9 Recent Advances in Nucleophilic Addition Reactions of Organoboronic Acids and Their Derivatives to Unsaturated C–N Functionalities 427 Timothy R. Ramadhar and Robert A. Batey

9.1 Introduction 427

9.2 Recent Advances in the Petasis Borono-Mannich Reaction 428

9.3 Reactions of N-Acyliminium Ions with Organoboronic Acids and Their Derivatives 449

9.4 Advances in Metal-Catalyzed Additions with Organoboronic Acids and Their Derivatives 455

9.5 Conclusions 472

References 473

10 Asymmetric Homologation of Boronic Esters with Lithiated Carbamates, Epoxides, and Aziridines 479 Matthew P. Webster and Varinder K. Aggarwal

10.1 Introduction 479

10.2 Lithiated Primary Alkyl Carbamates for the Homologation of Boranes and Boronic Esters 481

10.3 Lithiated Secondary Carbamates for the Homologation of Boranes and Boronic Esters 492

10.4 Benzylic N-Linked Lithiated Carbamates for the Homologation of Trialkylboranes 496

10.5 Lithiated Epoxides for the Homologation of Boronic Esters 496

10.6 Lithiated Aziridines for the Homologation of Boronic Esters 500

10.7 Conclusions 501

References 502

11 Organotrifluoroborates: Organoboron Reagents for the Twenty-First Century 507 Gary A. Molander and Ludivine Jean-Gérard

11.1 Introduction 507

11.2 Synthetic Approaches to Organotrifluoroborates 508

11.3 Elaboration of Organotrifluoroborates via Transformations of Pendant Functional Groups 509

11.4 Transition Metal-Catalyzed Processes 526

11.5 Miscellaneous Reactions of Organotrifluoroborates 537

11.6 Carbon–Carbon Bond-Forming Reactions with Activated Electrophiles 542

11.7 Conclusions 546

References 546

12 Borate and Boronic Acid Derivatives as Catalysts in Organic Synthesis 551 Joshua N. Payette and Hisashi Yamamoto

12.1 Introduction 551

12.2 Nonchiral Boron-Based Catalysis 551

12.3 Chiral Boron-Based Catalysis 561

12.4 Conclusion 587

References 587

13 Applications of Boronic Acids in Chemical Biology and Medicinal Chemistry 591 Nanting Ni and Binghe Wang

13.1 Introduction 591

13.2 Boronic Acids as Potential Medicinal Agents 591

13.3 Probes for Detecting Reactive Oxygen Species 597

13.4 MRI and PET Agents for in vivo Carbohydrate Imaging 603

13.5 Carbohydrate Biomarker Binding Agents and Sensors 607

13.6 Conclusions 617

References 617

14 Boronic Acids in Materials Chemistry 621 Jie Liu and John J. Lavigne

14.1 Introduction 621

14.2 Linear Boronate-Linked Materials 624

14.3 Macrocycles and Cages 637

14.4 Networks 658

14.5 Summary and Outlook 671

References 673

Index 677

Highly regioselective palladium-catalysed oxidative allylic C–H carbonylation of alkenes

Chem. Commun., 2011, 47, 12224-12226

Synergistic Palladium-Catalyzed C(sp3)[BOND]H Activation/C(sp3)[BOND]O Bond Formation: A Direct, Step-Economical Route to Benzolactones - Novák - 2011 - Angewandte Chemie International Edition - Wiley Online Library

1. 
   

2. Dr. Ruben Martin, ACIE, 2011,

DOI: 10.1002/anie.201105894