Catalytic, Asymmetric, Bromine-Induced Semipinacol Rearrangements at Unactivated Double Bonds

Abstract

A new catalyst system for the enantioselective bromine-induced semipinacol rearrangement of cyclic allylic alcohols is described. Using the commercially available (DHQD)₂Pyr catalyst the products containing an all-carbon quaternary chiral centre can be obtained in good yield and high enantioselectivity.

asymmetric catalysis - bromine - electrophilic addition - halogenation - rearrangement

References and Notes

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See Supporting Information for details. The complete crystallographic data can be obtained under the deposition numbers CCDC 835983 and 835982 from the Cambridge Crystallographic Data Centre.

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Considering Tu’s latest results^¹² one reviewer questioned the role of small amounts of water in the system. We used commercially available ‘dry’ solvents stored over molecular sieves for all reactions. The deliberate addition of 5 equivalents of water to the rearrangement of 1a under standard conditions did not change the enantioselectivity. Addition of methanol (5 equiv) or molecular sieves to the reaction was detrimental for the enantioselectivity (33% and 60% ee, respectively).

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