Rhodium-catalyzed enantioselective and diastereodivergent access to diaxially chiral heterocycles

Yishou Wang, Xiaohan Zhu, Deng Pan, Jierui Jing, Fen Wang (), Ruijie Mi, Genping Huang () and Xingwei Li ()
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Yishou Wang: Shandong University
Xiaohan Zhu: Shaanxi Normal University
Deng Pan: Tianjin University
Jierui Jing: Shaanxi Normal University
Fen Wang: Shaanxi Normal University
Ruijie Mi: Shandong University
Genping Huang: Tianjin University
Xingwei Li: Shandong University

Nature Communications, 2023, vol. 14, issue 1, 1-12

Abstract: Abstract N-N axially chiral biaryls represent a rarely explored class of atropisomers. Reported herein is construction of diverse classes of diaxially chiral biaryls containing N-N and C-N/C-C diaxes in distal positions in excellent enantioselectivity and diastereoselectivity. The N-N chiral axis in the products provides a handle toward solvent-driven diastereodivergence, as has been realized in the coupling of a large scope of benzamides and sterically hindered alkynes, affording diaxes in complementary diastereoselectivity. The diastereodivergence has been elucidated by computational studies which revealed that the hexafluoroisopropanol (HFIP) solvent molecule participated in an unusual manner as a solvent as well as a ligand and switched the sequence of two competing elementary steps, resulting in switch of the stereoselectivity of the alkyne insertion and inversion of the configuration of the C-C axis. Further cleavage of the N-directing group in the diaxial chiral products transforms the diastereodivergence to enantiodivergence.

Date: 2023
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DOI: 10.1038/s41467-023-39968-3

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