Cyclometalated Chiral-at-Ruthenium Catalyst for Enantioselective Ring-Closing C(sp(3))-H Carbene Insertion to Access Chiral Flavanones

Authors

Feng Han
Peter H. Choi
Chen-Xi Ye
Yvonne Grell
Xiulan Xie
Sergei I. Ivlev
Shuming Chen, Oberlin College

Abstract

A cyclometalated ruthenium complex with exclu-sively metal-centered chirality catalyzes the conversion of diazoketones to chiral flavanones with up to 99% yield and with up to 96% ee. A competing oxygen attack pathway involving the formation and [1,2]-shift (Stevens rearrangement) of an oxonium ylide intermediate was successfully suppressed in favor of a catalytic enantioselective ring-closing C(sp(3))-H carbene insertion. Density functional theory calculations provide a rationale for the observed C-H insertion over the undesirable C-O formation pathway. The method provides access to a variety of chiral flavanones which are considered privileged scaffolds with diverse biological activities.

Repository Citation

Han, Feng, Peter H. Choi, Chen-Xi, Ye, et al. 2022. "Cyclometalated Chiral-at-Ruthenium Catalyst for Enantioselective Ring-Closing C(sp(3))-H Carbene Insertion to Access Chiral Flavanones." ACS Catalysis 12(16): 10304-10312.

Publisher

American Chemical Society

Publication Date

8-19-2022

Publication Title

ACS Catalysis

Department

Chemistry and Biochemistry

Document Type

Article

DOI

10.1021/acscatal.2c02423

Keywords

Asymmetric catalysis, Cyclometalation, Chiral-at-metal, Stereogenic metal, Ruthenium, Carbene insertion, Flavanones

Language

English

Format

text