Catalytic Enantioselective (3+2) Annulations of Nucleophilic Thioacyl Rh(I)-Carbenes with Achmatowicz Rearrangement Products | ACS Catalysis

Catalytic Enantioselective (3+2) Annulations of Nucleophilic Thioacyl Rh(I)-Carbenes with Achmatowicz Rearrangement Products

Research Article May 28, 2024

Authors

Cunzhi Chen
Kang Lv
Youwei Chen
Hongguang Du
Jiaxi Xu
Tao Liu
Zhanhui Yang

ACS Catalysis

Cite this: ACS Catal. 2024, 14, 11, 8949–8957

Published May 28, 2024

Publication History

Received 11 May 2024
Accepted 16 May 2024
Revised 16 May 2024
Published online 28 May 2024
Published in issue 7 June 2024

Abstract

The cycloaddition and annulation reactions of Achmatowicz rearrangement products (ARPs) are critically important to the construction of molecular complexity and the total synthesis of natural products. However, this field is still blemished by the shortage of enantioselective (3+2) reactions of ARPs. Herein, we report the highly enantio-, diastereo-, and regioselective (3+2) annulations of ARPs with nucleophilic α-thioacyl Rh(I)-carbenes under Rh(I)/(R)-BINAP catalysis, producing bicyclic dihydrothiophenes with multiple functionalities, three continuous chiral centers, and five prochiral centers in up to 97% yields and 99:1 er. Mechanistically, the migratory insertion following anticoordination is suggested to determine the enantio- and regioselectivities and accounts for the nucleophilic character of α-thioacyl Rh(I)-carbenes. DFT calculations revealed that enantioinduction originates from the steric discrimination of (R)- and (S)-ARPs by the chiral ligand.

Subjects

Addition reactions
Annulations
Chemical reactions
Ligands
Stereoselectivity

Keywords

α-t