Transition-metal-free iterative two-fold reductive coupling and 1,3-borotropic shift to form 1,4-skipped dienes

Abstract

We report herein a transition-metal-free two-fold reductive coupling between prenal (allyl) tosylhydrazone and boronic acids/1,3-borotropic shift cascade to furnish 1,4-skipped dienes. In this work, a single batch operation produces (E,E)-1,4-skipped dienes by undergoing a second reductive coupling of the transient boronic acid, which developed in situ following the first reductive allylation and a cascade 1,3-boron migration. Remarkably, the protocol is compatible with various aryl- and alkyl-substituted boronic acids, is scalable and has demonstrated on 61 substrates with yields up to 98%.