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Cyclic alkenenitriles: synthesis, conjugate addition, and stereoselective annulation
Journal article   Peer reviewed

Cyclic alkenenitriles: synthesis, conjugate addition, and stereoselective annulation

Fraser F Fleming, Zhiyu Zhang, Qunzhao Wang and Omar W Steward
Journal of organic chemistry, v 68(20), pp 7646-7650
03 Oct 2003
DOI: https://doi.org/10.1021/jo0345291
PMID: 14510537
Featured in Collection :   UN Sustainable Development Goals @ Drexel

Abstract

Alkenes - chemistry Alkylation Chelating Agents - chemistry Cyclization Hydrocarbons, Cyclic - chemical synthesis Magnesium - chemistry Nitriles - chemistry Stereoisomerism
O-Alkylation of unsaturated silyl cyanohydrins with DMSO-Ac2O triggers a rearrangement to methylthiomethyl-protected hydroxyalkenenitriles that are easily hydrolyzed for subsequent annulations with omega-chloroalkyl Grignard reagents. Deprotonating the gamma-hydroxyalkenenitriles with t-BuMgCl followed by addition of omega-chloroalkyl Grignard reagents triggers a conjugate addition-alkylation sequence leading exclusively to cis-octalins, hydrindanes, and decalins. Stereoelectronic control favors an axial conjugate addition leading to a particularly reactive conformer that rapidly cyclizes to cis-fused bicyclic nitriles, whereas generating the ring-flipped conformer, through a stepwise sequence, allows access to the diastereomeric trans-decalin. Collectively, the rearrangement-annulation sequence represents the first general annulation of alkenenitriles to assemble diverse bicyclic nitriles with complete control over the two newly installed stereocenters.

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15 citations in Web of Science
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Web of Science research areas
Chemistry, Organic
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