Stereospecific Rhodium-Catalyzed Addition of Carboxylic Acids to gem -Difluoroallenes: Access to cis -1,1-Difluoroallyl Esters
Abstract
The gem -difluoroallylated scaffold holds a significant value in medicinal chemistry. However, stereoselective access to its cis -configured motif, thermodynamically disfavored over the trans isomer, remains a long-standing synthetic challenge. Herein, we report a rhodium(III)-catalyzed addition reaction of carboxylic acids to gem -difluoroallylations, which efficiently affords cis -1,1-difluoroallyl esters with high stereospecificity under ambient conditions. Mechanistic studies reveal that the bulky Cp*Rh(III) moiety dictates the stereochemical outcome via steric control during concerted difluoroallene coordination and carboxylate migration, where subsequent metal-centered protonation secures the exclusive cis configuration of the final gem -difluoroallylic products.
Fields of Study & Subjects
Fluorine in Organic Chemistry
Catalytic C–H Functionalization Methods
Inorganic Fluorides and Related Compounds
Publication details
- Journal / source
- Organic Letters
- Publisher
- American Chemical Society (ACS)
- Volume
- 28
- Issue
- 28
- Pages
- 9031–9036
- Publication date
- 4 July 2026
- Language
- EN