Selective E to Z isomerization of 1,3-Dienes Enabled by A Dinuclear Mechanism
Eiji Kudo, K. Sasaki, Shiori Kawamata, Kōji Yamamoto, Tetsuro Murahashi
Abstract
Abstract The E / Z stereocontrol in a C=C bond is a fundamental issue in olefin synthesis. Although the thermodynamically more stable E geometry is readily addressable by thermal Z to E geometric isomerization through equilibrium, it has remained difficult to undergo thermal geometric isomerization to the reverse E to Z direction in a selective manner, because it requires kinetic trapping of Z -isomer with injection of chemical energy. Here we report that a dinuclear Pd I −Pd I complex mediates selective isomerization of E -1,3-diene to its Z -isomer without photoirradiation, where kinetic trapping is achieved through rational sequences of dinuclear elementary steps. The chemical energy required for the E to Z isomerization can be injected from an organic conjugate reaction through sharing of common Pd species.