Synthesis 2017; 49(02): 440-450
DOI: 10.1055/s-0036-1588340
paper
© Georg Thieme Verlag Stuttgart · New York

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

Felicia Weber
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany   eMail: hilt@chemie.uni-marburg.de
,
Philipp S. Steinlandt
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany   eMail: hilt@chemie.uni-marburg.de
,
Monika Ballmann
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany   eMail: hilt@chemie.uni-marburg.de
,
Gerhard Hilt*
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany   eMail: hilt@chemie.uni-marburg.de
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Publikationsverlauf

Received: 10. Oktober 2016

Accepted: 13. Oktober 2016

Publikationsdatum:
14. November 2016 (online)


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

Supporting Information

 
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