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Synthesis 2019; 51(06): 1329-1341
DOI: 10.1055/s-0037-1611704
DOI: 10.1055/s-0037-1611704
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Zinc-Mediated Double Addition on Functionalized Nitriles
J. Caillé gratefully thanks the ‘Ministère de l’enseignement supérieur et de la recherche’ for a Ph.D. fellowship. M. Pantin thanks the ‘Université Bretagne Loire’ for a postdoctoral grant.Further Information
Publication History
Received: 29 October 2018
Accepted after revision: 26 November 2018
Publication Date:
24 January 2019 (online)


Abstract
Allylzinc reagents were used to access highly functionalized tertiary carbinamine derivatives in high yields from cyanoesters and cyanocarbonates. While the monoaddition of organometallics on nitriles is generally observed, in this work the nucleophilic allylation occurs twice, due to an intermediate transfer of the carbonyl moiety onto the nitrogen atom. The chemoselectivity of the reaction allows the presence of various functionalities and in the case of carbonate derivatives, the nature of the final product was modulated by kinetic control, giving selectively hydroxyamides or cyclic carbamates.
Key words
allylation - nitriles - nucleophilic addition - organometallic reagents - tertiary carbinamines - zincSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611704.
- Supporting Information