In recent years, transition metal-catalyzed direct (hetero)arylation reactions of heteroarenes with (hetero)aryl halides and pseudohalides have received significant attention as eco-friendly and economic alternatives to classical methods for the construction of heteroaryl-(hetero)aryl CC bonds by transition metal-catalyzed cross-couplings involving the use of stoichiometric amounts of organometallic reagents. This critical review with 430 references covers the results obtained in the period January 2009 to February 2013 in the area of the transition metal-catalyzed direct inter- and intramolecular (hetero)arylation reactions of heteroarenes containing one heteroatom. Particular attention has been given to illustrate chemo- and site selectivity aspects of these reactions as well applications of these CC bond forming reactions in the synthesis of pharmaceutically relevant compounds, natural products and their analogues and precursors. The most recent advancements into the mechanism(s) of these reactions have also been briefly reported.

Cross‐Coupling of Heteroarenes by CH Functionalization: Recent Progress towards Direct Arylation and Heteroarylation Reactions Involving Heteroarenes Containing One Heteroatom

Advances in the chemical synthesis of C-pyranosides/furanosides are summarized, covering the literature from 2000 to 2016. The majority of the methods take advantage of the construction of the glycosidic C—C bond. These C-glycosylation methods are categorized herein in terms of the glycosyl donor precursors, which are commonly used in O-glycoside synthesis and are easily accessible to nonspecialists. They include glycosyl halides, glycals, sugar acetates, sugar lactols, sugar lactones, 1,2-anhydro sugars, thioglycosides/sulfoxides/sulfones, selenoglycosides/telluroglycosides, methyl glycosides, and glycosyl imidates/phosphates. Mechanistically, C-glycosylation reactions can involve glycosyl electrophilic/cationic species, anionic species, radical species, or transition-metal complexes, which are discussed as subcategories under each type of sugar precursor. Moreover, intramolecular rearrangements, such as the Claisen rearrangement, Ramberg–Backlund rearrangement, and 1,2-Wittig rearrangement, which usuall...

Recent Advances in the Chemical Synthesis of C-Glycosides

Investigation of new methods for the synthesis of C–C bonds is fundamental for the development of new organic drugs and materials. Aryl-, alkenyl- and alkynylboronic acids and their derivatives constitute attractive reagents towards this end, due to their stability, low toxicity and ease of handling. However, these compounds are only moderately nucleophilic. Consequently, the most popular C–C bond forming reactions of these boronic acids, such as the Suzuki–Miyaura, Heck, and Hayashi–Miyaura reactions, or additions to CO and CN bonds, require catalysis by transition metals. However, due to the toxicity and cost of transition metals, some new methods for C–C bond formation using aryl-, alkenyl- and alkynylboronic acids under transition-metal-free conditions are beginning to emerge. In this tutorial review, the recent synthetic advances in this field are highlighted and discussed.

Transition-metal-free C-C bond forming reactions of aryl, alkenyl and alkynylboronic acids and their derivatives.

Recent Developments in the Ferrier Rearrangement

Regioselective Metal-Free Cross-Coupling of Quinoline N-Oxides with Boronic Acids

Nucleophilic Addition of Potassium Alkynyltrifluoroborates to d-Glucal Mediated by BF3·OEt2: Highly Stereoselective Synthesis of α-C-glycosides

The Suzuki–Miyaura cross-coupling reaction of 2-(butyltellanyl) or 2,5-bis-(butyltellanyl)furans and thiophenes with potassium aryltrifluoroborate salts catalyzed by palladium afforded 2-aryl- or 2,5-diaryl-furans and thiophenes in moderate to good yields.

Thomas L. S. Hough

Papers

Nucleophilic Addition of Potassium Alkynyltrifluoroborates to d-Glucal Mediated by BF3·OEt2: Highly Stereoselective Synthesis of α-C-glycosides

Synthesis of 2-Aryl- and 2,5-Diarylfurans and Thiophenes by Suzuki-Miyaura Reactions Using Potassium Trifluoroborate Salts and Heteroaryltellurides

Nucleophilic Addition of Potassium Alkynyltrifluoroborates to D‐Glucal Mediated by BF3·OEt2: Highly Stereoselective Synthesis of α‐C‐Glycosides.

Synthesis of 2-Aryl- and 2,5-Diarylfurans and Thiophenes by Suzuki—Miyaura Reactions Using Potassium Trifluoroborate Salts and Heteroaryltellurides.