Journal article
Cyclic nitriles: Stereodivergent addition-alkylation-cyclization to cis- and trans-abietanes
Journal of organic chemistry, v 73(10), pp 3674-3679
16 May 2008
PMID: 18416532
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
Diverse cyclic hydroxy nitrile's are readily synthesized through sequential 1,2-1,4-Grignard addition-methylations to 3-oxo-1-cyclohexene-1-carbonitrile. Acid-catalyzed intramolecular cyclizations of the cyclic hydroxy nitriles reveal fundamental stereoselectivity trends in Friedel-Crafts cyclizations to cis- and trans-abietanes. In contrast to previous assumptions, comparative cationic cyclizations with electron-rich and electron-poor aromatic nucleophiles exhibit similar preferences for cyclization to cis-abietanes. Optimizing the cyclizations for trans-abietanes has identified ZrCl4 as an exceptional Lewis acid which, for cyclizations of iminolactones, favors trans-abietanes as the only observable diastereomer. The sequential oxonitrile addition-Friedel-Crafts cyclization strategy provides a rapid, stereodivergent synthesis of cis- or trans-abietanes, demonstrates the dramatic influence of ZrCl4 in promoting cationic cyclizations, and in contrast to previous assumptions suggests that the cyclization stereoselectivity is not correlated with the electronic nature of the aromatic nucleus.
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Details
- Title
- Cyclic nitriles: Stereodivergent addition-alkylation-cyclization to cis- and trans-abietanes
- Creators
- Fraser F. Fleming - Duquesne UniversityGuoqing Wei - Duquesne UniversityOmar W. Steward - Duquesne University
- Publication Details
- Journal of organic chemistry, v 73(10), pp 3674-3679
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 6
- Grant note
- 2 R15 AI 051352 / NIAID NIH HHS; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA; NIH National Institute of Allergy & Infectious Diseases (NIAID) 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)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000255698500002
- Scopus ID
- 2-s2.0-43449098549
- Other Identifier
- 991020898497804721
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InCites Highlights
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- Web of Science research areas
- Chemistry, Organic