Structure-Dependent Nickel-Catalysed Transposition of N-Allylamides to E- or Z-Enamides

Dedicated to Prof. Dieter Enders on the occasion of his 70^th birthday

Abstract

The nickel-catalysed transposition of a carbon–carbon double bond of N-allyl and N-homoallyl amides is described. While the transposition of acyclic amides gave very high Z-selectivity of the enamides, corresponding cyclic N-allyl amides led exclusively to the E-configured products. Thereby, we realised a stereodivergent approach to enamides that is dependent on the structure of the amide substituents. When homoallylic substrates are used, a temperature-controlled single transposition to a Z-allylic amide derivative at low temperature or a double transposition to an E-enamide at elevated temperature could be achieved.

Key words

allyl amides - double bond translocation - enamides - nickel - stereoselectivity

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