Indole‐Quinoline Transmutation Enabled by a Formal Rhodium Carbynoid

L Lu‐Jie Liu (Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China) M Meng‐Yang Tian (Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China) Z Zhi‐Yu Lang (Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China) Y Yong‐Li Wang (Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China) C Chun‐Yang He (Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China) Y Yong‐Zheng Chen (Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China) W Wen‐Yong Han (Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China)

Abstract

Abstract Skeleton editing is an emerging and powerful tool in organic chemistry because it can simplify synthetic procedures towards complex molecules. Herein, we present an approach for indole‐quinoline transmutation through rhodium‐catalyzed single‐carbon insertion into the C2( sp 2 )─C3( sp 2 ) bond of an indole with an α‐diazotrifluoroethyl sulfonium salt that we developed. This protocol involves a formal trifluoromethyl rhodium carbynoid (CF 3 C + = Rh) resembling a trifluoromethyl cationic carbyne (CF 3 C + :), allowing facile access to an array of quinolines in moderate to high yields. Potential applications in the late‐stage skeletal editing of pharmaceutical and natural product derivatives, preparation of adapalene analogs, scaled‐up synthesis, and transformations of products are highlighted. Finally, a computational study was conducted to support the envisioned mechanism.

Article Details

Volume / Issue Vol. 64, Issue 25
Published June 17, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (7)

L

Lu‐Jie Liu

Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China

M

Meng‐Yang Tian

Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China

Z

Zhi‐Yu Lang

Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China

Y

Yong‐Li Wang

Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China

C

Chun‐Yang He

Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China

Y

Yong‐Zheng Chen

Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China

W

Wen‐Yong Han

Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals School of Pharmacy Zunyi Medical University No. 6 West Xuefu Rd Zunyi 563006 China