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The significance of degenerate processes to enantioselective olefin metathesis reactions promoted by stereogenic-at-Mo complexes.

Publication ,  Journal Article
Meek, SJ; Malcolmson, SJ; Li, B; Schrock, RR; Hoveyda, AH
Published in: Journal of the American Chemical Society
November 2009

The present study provides spectroscopic and experimental evidence demonstrating that degenerate metathesis is critical to the effectiveness of this emerging class of chiral catalysts. Isolation and X-ray characterization of both diastereomeric complexes, as well as an examination of the reactivity and enantioselectivity patterns exhibited by such initiating neophylidenes in promoting ring-closing metathesis processes, are disclosed. Only when sufficient amounts of ethylene are generated and inversion at Mo through degenerate processes occurs at a sufficiently rapid rate is high enantioselectivity achieved, irrespective of the stereochemical identity of the initiating alkylidene (Curtin-Hammett kinetics). With diastereomeric metal complexes that undergo rapid interconversion, stereomutation at the metal center becomes inconsequential, and stereoselective synthesis of a chiral catalyst is not required.

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

November 2009

Volume

131

Issue

45

Start / End Page

16407 / 16409

Related Subject Headings

  • Stereoisomerism
  • Organometallic Compounds
  • Molybdenum
  • Molecular Structure
  • Models, Molecular
  • General Chemistry
  • Crystallography, X-Ray
  • Alkenes
  • 40 Engineering
  • 34 Chemical sciences
 

Citation

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Meek, S. J., Malcolmson, S. J., Li, B., Schrock, R. R., & Hoveyda, A. H. (2009). The significance of degenerate processes to enantioselective olefin metathesis reactions promoted by stereogenic-at-Mo complexes. Journal of the American Chemical Society, 131(45), 16407–16409. https://doi.org/10.1021/ja907805f
Meek, Simon J., Steven J. Malcolmson, Bo Li, Richard R. Schrock, and Amir H. Hoveyda. “The significance of degenerate processes to enantioselective olefin metathesis reactions promoted by stereogenic-at-Mo complexes.Journal of the American Chemical Society 131, no. 45 (November 2009): 16407–9. https://doi.org/10.1021/ja907805f.
Meek SJ, Malcolmson SJ, Li B, Schrock RR, Hoveyda AH. The significance of degenerate processes to enantioselective olefin metathesis reactions promoted by stereogenic-at-Mo complexes. Journal of the American Chemical Society. 2009 Nov;131(45):16407–9.
Meek, Simon J., et al. “The significance of degenerate processes to enantioselective olefin metathesis reactions promoted by stereogenic-at-Mo complexes.Journal of the American Chemical Society, vol. 131, no. 45, Nov. 2009, pp. 16407–09. Epmc, doi:10.1021/ja907805f.
Meek SJ, Malcolmson SJ, Li B, Schrock RR, Hoveyda AH. The significance of degenerate processes to enantioselective olefin metathesis reactions promoted by stereogenic-at-Mo complexes. Journal of the American Chemical Society. 2009 Nov;131(45):16407–16409.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

November 2009

Volume

131

Issue

45

Start / End Page

16407 / 16409

Related Subject Headings

  • Stereoisomerism
  • Organometallic Compounds
  • Molybdenum
  • Molecular Structure
  • Models, Molecular
  • General Chemistry
  • Crystallography, X-Ray
  • Alkenes
  • 40 Engineering
  • 34 Chemical sciences