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Cyclic nitriles: diastereoselective alkylations
Journal article   Peer reviewed

Cyclic nitriles: diastereoselective alkylations

Fraser F Fleming, Subrahmanyam Gudipati, Zhiyu Zhang, Wang Liu and Omar W Steward
Journal of organic chemistry, v 70(10), pp 3845-3849
13 May 2005
PMID: 15876069

Abstract

[reaction: see text] Diastereoselective alkylations of metalated conformationally locked 4-tert-butylcyclohexanecarbonitrile are highly diastereoselective with magnesium and copper counterions but only modestly diastereoselective with lithium as the counterion. Selective generation of diverse metalated nitriles is readily achieved through bromine-magnesium, -copper, and -lithium exchange reactions of the corresponding bromonitrile or, for lithium, by deprotonating the parent nitrile with lithium diethylamide. Collectively, high alkylation stereoselectivities correlate with the retentive alkylations of C-metalated nitriles, whereas N-lithiated nitriles alkylate with modest selectivity, reflecting minimal steric differences in the corresponding axial and equatorial electrophile trajectories.

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Web of Science research areas
Chemistry, Organic
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