Stereoconvergent Synthesis of Z-1,3-Disubstituted-1,3-Dienes by Uphill Photocatalysis.

Abstract

A variety of 1-aryl-1,3-dienes were isomerized from E to Z isomers by photocatalysis using Ru(bpy)3 [PF6 ]2 and blue LED light. Enrichment of the Z-isomer is thought to occur by selective triplet energy transfer from the photocatalyst to the stereoisomeric mixture. The 1,3-diene starting materials are easily made by catalytic ene-yne metathesis (EYM). To access 1,3-diene Z-stereoisomers directly, a one pot procedure was developed. Additional 1,3-dienes were investigated for both isomerization and Z-enrichment. The combination of cross EYM with photocatalysis allows for the stereoconvergent synthesis of Z-1,3-dienes.