摘要：

The combination of gold(I) and enzyme catalysis has been exhaustively analysed aiming to develop a two﹕tep concurrent approach. This strategy consists of a Meyer㏒chuster rearrangement of a series of easily available propargylic alcohols followed by the stereoselective bioreduction of the corresponding allylic ketone intermediates, providing optically pure β,βヾisubstituted allylic alcohols. Thus, the first concurrent cascade example involving the use of a gold N﹉eterocyclic carbene and an enzyme is described, demonstrating the compatibility of both catalyst types in aqueous medium under very mild conditions. The combination of [1,3‐bis(2,6ヾiisopropylphenyl)imidazollidene][bis(trifluoromethanesulfonyl)﹊mide]gold(I) (IPrAuNTf 2 ) and a selective alcohol dehydrogenase (ADH〢 from Rhodococcus ruber , KRED㏄1〢12 or KRED㏄3〨09), has allowed the synthesis of a series of optically active ( E )rylpentnls in good isolated yields (65%). The chemoenzymatic approach was also successfully extended to various 2﹉etarylpentnl, hexynol and butynol derivatives. Remarkably, the use of alcohol dehydrogenases of opposite selectivity has allowed the straightforward production of both allyl alcohol enantiomers (93gt;99% ee ) for a broad panel of substrates bearing different substitutions in the aromatic ring.

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