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Transition-metal-free iterative two-fold reductive coupling and 1,3-borotropic shift to form 1,4-skipped dienes
Kasarla Varalaxmi1,2, Kangkan Pradhan1,3, Hasina Mamataj Begam1
1Organic and Medicinal Chemistry Division, CSIR-Indian Institute of Chemical Biology, 4 Raja S. C. Mullick Road, Jadavpur, Kolkata-700032, West Bengal, India. rjana@iicb.res.in.
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%.
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