Journal article
Metalated nitriles: Internal 1,2-asymmetric induction
Journal of organic chemistry, v 73(7), pp 2803-2810
04 Apr 2008
PMID: 18336042
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
Alkylations of conformationally constrained acyclic nitriles containing vicinal dimethyl groups and an adjacent phenyl group or trisubstituted alkene are exceptionally diastereoselective. Probing the alkylation stereoselectivity with a series of C- and N-metalated nitriles implicates a reactive conformation in which an sp(2)-hybridized substituent projects over the metalated nitrile to avoid allylic strain. Steric screening thereby directs the electrophilic attack to the face of the metalated nitrile opposite the projecting substituent. Excellent stereoselectively is maintained in a diverse range of alkylations that efficiently install quaternary centers, even with isopropyliodide in which a contiguous array of tertiary-quaternary-tertiary stereocenters is created! Screening the conformational requirements with a series of acyclic nitriles and esters reveals the key structural requirements for high selectivity while providing a robust, predictive model that accounts for comparable ester alkylations affording the opposite diastereomer! The intensive survey of metalated nitrile alkylations identifies the key structural features required for high 1,2-asymmetric induction, addresses the long-standing challenge of asymmetric alkylations with acylic metalated nitriles, and provides a versatile method for installing hindered quaternary centers with excellent stereocontrol.
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Details
- Title
- Metalated nitriles: Internal 1,2-asymmetric induction
- Creators
- Fraser F. Fleming - Duquesne UniversityWang Liu - Duquesne UniversitySomraj Ghosh - Duquesne UniversityOmar W. Steward - Duquesne University
- Publication Details
- Journal of organic chemistry, v 73(7), pp 2803-2810
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 8
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000254544800040
- Scopus ID
- 2-s2.0-41649084196
- Other Identifier
- 991020898392604721
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InCites Highlights
Data related to this publication, from InCites Benchmarking & Analytics tool:
- Web of Science research areas
- Chemistry, Organic