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Journal article
Metalated nitriles: stereodivergent cation-controlled cyclizations
Tetrahedron, v 64(32), pp 7477-7488
04 Aug 2008
PMID: 19657380
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
Stereodivergent cyclizations of gamma-hydroxy cyclohexanecarbonitriles are controlled simply through judicious choice of cation in the alkylmetal base. Deprotonating a series of cyclic gamma-hydroxy nitriles with i-PrMgBr generates C-magnesiated nitriles that cyclize under stereoelectronic control to cis-fused hydrindanes, decalins, and bicyclo[5.4.0]undecanes. An analogous deprotonation with BuLi triggers cyclization to traps-fused hydrindanes, decalins, and bicyclo[5.4.0]undecanes consistent with a sterically controlled electrophilic attack on an equatorial nitrile anion. Using cations to control the geometry of metalated nitriles provides a versatile, stereodivergent cyclization to cis- and traps-hydrindanes, decalins, and [5.4.0]undecanes, and reveals the key geometric requirements for intramolecular S(N)2 and S(N)2(') displacements. (C) 2008 Elsevier Ltd. All rights reserved.
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Details
- Title
- Metalated nitriles: stereodivergent cation-controlled cyclizations
- Creators
- Fraser F. Fleming - Duquesne UniversityYunjing Wei - Duquesne UniversityWang Liu - Duquesne UniversityZhiyu Zhang - Duquesne University
- Publication Details
- Tetrahedron, v 64(32), pp 7477-7488
- Publisher
- Elsevier
- Number of pages
- 12
- Grant note
- R15AI051352 / NATIONAL INSTITUTE OF ALLERGY AND INFECTIOUS DISEASES; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA; NIH National Institute of Allergy & Infectious Diseases (NIAID) R15 AI051352; R15 AI051352-02 / NIAID NIH HHS; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA; NIH National Institute of Allergy & Infectious Diseases (NIAID)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000257912200002
- Scopus ID
- 2-s2.0-45549122288
- Other Identifier
- 991020898500104721
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Data related to this publication, from InCites Benchmarking & Analytics tool:
- Web of Science research areas
- Chemistry, Organic