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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.

Selective E to Z isomerization of 1,3-Dienes Enabled by A Dinuclear Mechanism