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Enol Ethers as Substrates for Efficient Z- and Enantioselective Ring-Opening/Cross-Metathesis Reactions Promoted by Stereogenic-at-Mo Complexes; Utility in Chemical Synthesis and Mechanistic Attributes
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, United States.
Boston Coll, Merkert Chem Ctr, Dept Chem, Chestnut Hill, MA 02467 USA.
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, United States.
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, United States.
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2012 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 134, no 5, 2788-2799 p.Article in journal (Refereed) Published
Abstract [en]

The first examples of catalytic enantioselective ring-opening/cross- metathesis (EROCM) reactions that involve enol ethers are reported. Specifically, we demonstrate that catalytic EROCM of several oxa-and azabicycles, cyclobutenes and a cyclopropene with an alkyl-or aryl-substituted enol ether proceed readily in the presence of a stereogenic-at-Mo monopyrrolide-monoaryloxide. In some instances, as little as 0.15 mol % of the catalytically active alkylidene is sufficient to promote complete conversion within 10 min. The desired products are formed in up to 90% yield and >99:1 enantiomeric ratio (er) with the disubstituted enol ether generated in >90% Z selectivity. The enol ether of the enantiomerically enriched products can be easily differentiated from the terminal alkene through a number of functionalization procedures that lead to the formation of useful intermediates for chemical synthesis (e.g., efficient acid hydrolysis to afford the enantiomerically enriched carboxaldehyde). In certain cases, enantioselectivity is strongly dependent on enol ether concentration: larger equivalents of the cross partner leads to the formation of products of high enantiomeric purity (versus near racemic products with one equivalent). The length of reaction time can be critical to product enantiomeric purity; high enantioselectivity in reactions that proceed to >98% conversion in as brief a reaction time as 30 s can be nearly entirely eroded within 30 min. Mechanistic rationale that accounts for the above characteristics of the catalytic process is provided. © 2012 American Chemical Society.

Place, publisher, year, edition, pages
2012. Vol. 134, no 5, 2788-2799 p.
Keyword [en]
Catalysis; Crystallography, X-Ray; Ethers; Models, Molecular; Molecular Structure; Molybdenum; Organometallic Compounds; Stereoisomerism
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:miun:diva-18085DOI: 10.1021/ja210946zISI: 000300460600053Scopus ID: 84856700233OAI: oai:DiVA.org:miun-18085DiVA: diva2:580137
Available from: 2012-12-20 Created: 2012-12-20 Last updated: 2014-08-29Bibliographically approved

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Ibrahem, IsmailSchrock, R.Hoveyda, H
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