Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis

Catalytic carbene insertion into C-H bonds.

Isolation and synthesis of biologically active carbazole alkaloids

Binaphthol-derived phosphoric acid as a versatile catalyst for enantioselective carbon–carbon bond forming reactions

The functionalization of C(sp3 )-H bonds streamlines chemical synthesis by allowing the use of simple molecules and providing novel synthetic disconnections. Intensive recent efforts in the development of new reactions based on C-H functionalization have led to its wider adoption across a range of research areas. This Review discusses the strengths and weaknesses of three main approaches: transition-metal-catalyzed C-H activation, 1,n-hydrogen atom transfer, and transition-metal-catalyzed carbene/nitrene transfer, for the directed functionalization of unactivated C(sp3 )-H bonds. For each strategy, the scope, the reactivity of different C-H bonds, the position of the reacting C-H bonds relative to the directing group, and stereochemical outcomes are illustrated with examples in the literature. The aim of this Review is to provide guidance for the use of C-H functionalization reactions and inspire future research in this area.

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Complementary Strategies for Directed C(sp3 )-H Functionalization: A Comparison of Transition-Metal-Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer.

Rhodium catalyzed reactions of diazo compounds form a powerful set of tools for synthetic organic chemists. Reactivity modes include cyclopropanation, C-H insertion, X-H insertion, and ylide formation. A myriad of factorsinfluences the mode of reaction, selectivity, and yield for these reaction processes. This review examines the subtle electronic, steric and conformational effects that in turn have profound impacts on reaction paths and selectivity. 1 Introduction 2 Achiral Rhodium(II) Catalysts 2.1 Effect of Catalyst Electrophilicity on Selectivity 2.2 Effect of Diazo Substitution on Selectivity 2.3 Effect of Substrate Substitution on Selectivity 3 Chiral Rhodium(II) Catalysts 3.1 Carboxylate Ligands 3.2 Carboxamidate Ligands 3.3 Phosphate Ligands 3.4 Phosphine Ligands 4 Conclusions.

Selectivity in Rhodium(II) Catalyzed Reactions of Diazo Compounds: Effects of Catalyst Electrophilicity, Diazo Substitution, and Substrate Substitution. From Chemoselectivity to Enantioselectivity

Benzannulation reactions of Fischer carbene complexes for the synthesis of indolocarbazoles

The synthesis of indolocarbazoles was achieved via photochemical and thermal annulation reactions of chromium Fischer carbene complexes. This methodology allows for facile incorporation of hydrogen bonding functionality which complements the pharmacophore contained within bioactive indolocarbazole natural products.

Andrea L. Zechman

Papers

Selectivity in Rhodium(II) Catalyzed Reactions of Diazo Compounds: Effects of Catalyst Electrophilicity, Diazo Substitution, and Substrate Substitution. From Chemoselectivity to Enantioselectivity

Benzannulation reactions of Fischer carbene complexes for the synthesis of indolocarbazoles

Selectivity in Rhodium(II) Catalyzed Reactions of Diazo Compounds: Effects of Catalyst Electrophilicity, Diazo Substitution, and Substrate Substitution. From Chemoselectivity to Enantioselectivity

Benzannulation Reactions of Fischer Carbene Complexes for the Synthesis of Indolocarbazoles.