Rhodium/Amine Dual Catalytic System for Reassembling CC Bonds of Conjugated Alkynes with Cyclopropenes via Cutting/ Insertion Cascade

Amines are powerful organocatalysts that are well-documented in catalyzing carbonyl compounds to realize trans-formations. However, they are rarely applied in alkyne activations. Herein, we disclose an efficient amine/Rh(II) dual catalytic system to reassemble the CC bond of conjugated alkynes with cyclopropenes, which enables construction of alpha-vinyldicarbonyl derivatives under very mild reaction conditions. Vinyl cyclopropylamines might be involved as key intermediates through ring-opening of cyclopropenes, catalytic amination of alkynes, and tandem cyclopropantion sequences in high atom and step-economies. This formal cutting/insertion cascade platform is compatible with a broad substrate scope including complex natural and unnatural molecules for late-stage functionalization.

Automated summary

In this study, we describe an efficient amine/Rh(II) dual catalytic system that enables the reassembly of conjugated alkynes with cyclopropenes, resulting in the construction of alpha-vinyldicarbonyl derivatives under mild reaction conditions. This cascade platform offers high atom and step economies, and is compatible with a broad range of substrates including complex natural and unnatural molecules for late-stage functionalization.