Rearrangement of Allylic Acetates

By: Josephine Nakhla, Aldrich ChemFiles 2009, 9.2, 16.

Aldrich ChemFiles 2009, 9.2, 16.

Marion and co-workers reported the first rearrangement of allylic acetates using a gold catalyst ligated to an N-heterocyclic carbene ligand. A bulky ligand bound to the gold catalyst proved imperative to this approach. The catalyst system was found to be highly versatile, providing a variety of rearranged primary oxo derivatives in good yield, either under thermal or microwave conditions (Scheme 2). In addition, the scope was found to be quite broad for a wide variety of allylic acetates. The authors propose a mechanism akin to that described by Overman, Henry, and Hartwig for analogous allylic rearrangments with Hg and Pd (cyclization-induced rearrangement-Scheme 3).1

Scheme 2.

Scheme 3.

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  1. Marion, N. et al. Org. Lett. 2007, 9, 2653.

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