Transition-metal-catalyzed enantioselective C-H functionalization has become a powerful strategy for the formation of C-C or C-X bonds, enabling the highly asymmetric synthesis of a wide range of enantioenriched compounds. Atropisomers are widely found in natural products and pharmaceutically relevant molecules, and have also found applications as privileged frameworks for chiral ligands and catalysts. Thus, research into asymmetric routes for the synthesis of atropisomers has garnered great interest in recent years. In this regard, transition-metal-catalyzed enantioselective C-H functionalization has emerged as an atom-economic and efficient strategy toward their synthesis. In this Perspective, the approaches for the synthesis of atropisomers by transition-metal-catalyzed asymmetric C-H functionalization reactions are summarized. The main focus here is on asymmetric catalysis via Pd, Rh, and Ir complexes, which have been the most frequently utilized catalysts among reported enantioselective C-H functionalization reactions. Finally, we discuss limitations on available protocols and give an outlook on possible future avenues of research.

Synthesis of Atropisomers by Transition-Metal-Catalyzed Asymmetric C-H Functionalization Reactions.

Palladium-catalyzed enantioselective C–H functionalization via C–H palladation

Axially chiral aldehydes have received increasing attention in enantioselective catalysis. However, only very few catalytic methods have been developed to construct structurally diverse axially chiral aldehydes. We herein describe an NHC-catalyzed atroposelective esterification of biaryl dialdehydes as a general and practical strategy for the construction of axially chiral aldehydes. Mechanistic studies indicate that coupling proceeds through a novel combination of NHC-catalyzed desymmetrization of the dialdehydes and kinetic resolution. This protocol features excellent enantioselectivity, mild conditions, good functional-group tolerance, and applicability to late-stage functionalization and provides a modular platform for the synthesis of axially chiral aldehydes and their derivatives.

Synthesis of Axially Chiral Aldehydes by N-Heterocyclic-Carbene-Catalyzed Desymmetrization Followed by Kinetic Resolution.

C–H bond functionalization by high-valent cobalt catalysis: current progress, challenges and future perspectives

The catalytic asymmetric construction of N-N atropisomeric biaryls remains a formidable challenge. Studies of them lag far behind studies of the more classical carbon-carbon biaryl atropisomers, hampering meaningful development. Herein, the first palladium-catalyzed enantioselective C-H activation of pyrroles for the synthesis of N-N atropisomers is presented. Structurally diverse indole-pyrrole atropisomers possessing a chiral N-N axis were produced with good yields and high enantioselectivities by alkenylation, alkynylation, allylation, or arylation reactions. Furthermore, the kinetic resolution of trisubstituted N-N heterobiaryls with more sterically demanding substituents was also achieved. Importantly, this versatile C-H functionalization strategy enables iterative functionalization of pyrroles with exquisite selectivity, expediting the formation of valuable, complex, N-N atropisomers.

Enantioselective Synthesis of N-N Atropisomers by Palladium-Catalyzed C-H Functionalization of Pyrroles.

The merging of C–H and C–C bond cleavage into one single chemical process remains a daunting challenge, especially in an asymmetric manner. Herein, a Pd(II)-catalyzed enantioselective tandem C–H/C–...

https://www.chinesechemsoc.org/doi/pdf/10.31635/ccschem.021.202000695

Merging C–H and C–C Activation in Pd(II)-Catalyzed Enantioselective Synthesis of Axially Chiral Biaryls

Thioamide-Directed Cp*Co(III)-Catalyzed C-H Allylation of Ferrocenes

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Merging C–H and C–C Activation in Pd(II)-Catalyzed Enantioselective Synthesis of Axially Chiral Biaryls

Thioamide-Directed Cp*Co(III)-Catalyzed C-H Allylation of Ferrocenes