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Electrophile-Dependent Alkylations of Lithiated 4-Alkoxyalk-4-enenitriles
Journal article   Peer reviewed

Electrophile-Dependent Alkylations of Lithiated 4-Alkoxyalk-4-enenitriles

Bhaskar R. Pitta, Omar W. Steward and Fraser F. Fleming
Journal of organic chemistry, v 83(5), pp 2753-2762
02 Mar 2018
PMID: 29432696

Abstract

Chemistry Chemistry, Organic Physical Sciences Science & Technology
Alkylations of acyclic, lithiated 4-alkoxyalk-4-enenitriles are highly diastereoselective with an unusual electrophile-dependent preference. Alkyl halides, sulfur, chlorine, and acyl cyanide electrophiles intercept a series of lithiated 4-alkoxyalk-4-enenitriles to install contiguous tertiary-quaternary stereocenters with high diastereoselectivity, whereas acylations with ester and carbonate electrophiles are modestly selective. The diastereoselectivity is consistent with electrophilic attack on the most accessible face of the lithated nitrile for most electrophiles except ester and carbonate electrophiles, which likely precoordinate the lithiated nitrile before acylation. Intercepting the lithiated 4-alkoxyalk-4-enenitriles with a range of electrophiles provide insight into the criteria for otherwise challenging diastereoselective alkylations and acylations of acyclic nitriles.

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Collaboration types
Domestic collaboration
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Web of Science research areas
Chemistry, Organic
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