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Enantioselective synthesis of cyclic enol ethers and all-carbon quaternary stereogenic centers through catalytic asymmetric ring-closing metathesis.

Publication ,  Journal Article
Lee, A-L; Malcolmson, SJ; Puglisi, A; Schrock, RR; Hoveyda, AH
Published in: Journal of the American Chemical Society
April 2006

The first examples of catalytic asymmetric ring-closing metathesis (ARCM) reactions of enol ethers are reported. To identify the most effective catalysts, various chiral Mo- and Ru-based catalysts were screened. Although chiral Ru catalysts (those that do not bear a phosphine ligand) promote ARCM in some cases, such transformations proceed in <10% ee. In contrast, Mo-based alkylidenes give rise to efficient ARCM and deliver the desired products in the optically enriched form. Thus, Mo-catalyzed enantioselective transformations allow access to various five- and six-membered cyclic enol ethers in up to 94% ee from readily available achiral starting materials. The first examples of catalytic ARCM that lead to the formation of all-carbon quaternary stereogenic centers are also disclosed. Mechanistic models that offer a plausible rationale for the identity of major enantiomers as well as the observed levels of enantioselectivity are provided. Representative examples demonstrate that the enol ether moiety and the unreacted alkene of the ARCM products can be discriminated with excellent site selectivity (>98%).

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

April 2006

Volume

128

Issue

15

Start / End Page

5153 / 5157

Related Subject Headings

  • Stereoisomerism
  • Models, Molecular
  • General Chemistry
  • Ethers, Cyclic
  • Cycloparaffins
  • Cyclization
  • Catalysis
  • Alkenes
  • 40 Engineering
  • 34 Chemical sciences
 

Citation

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Lee, A.-L., Malcolmson, S. J., Puglisi, A., Schrock, R. R., & Hoveyda, A. H. (2006). Enantioselective synthesis of cyclic enol ethers and all-carbon quaternary stereogenic centers through catalytic asymmetric ring-closing metathesis. Journal of the American Chemical Society, 128(15), 5153–5157. https://doi.org/10.1021/ja058428r
Lee, Ai-Lan, Steven J. Malcolmson, Alessandra Puglisi, Richard R. Schrock, and Amir H. Hoveyda. “Enantioselective synthesis of cyclic enol ethers and all-carbon quaternary stereogenic centers through catalytic asymmetric ring-closing metathesis.Journal of the American Chemical Society 128, no. 15 (April 2006): 5153–57. https://doi.org/10.1021/ja058428r.
Lee A-L, Malcolmson SJ, Puglisi A, Schrock RR, Hoveyda AH. Enantioselective synthesis of cyclic enol ethers and all-carbon quaternary stereogenic centers through catalytic asymmetric ring-closing metathesis. Journal of the American Chemical Society. 2006 Apr;128(15):5153–7.
Lee, Ai-Lan, et al. “Enantioselective synthesis of cyclic enol ethers and all-carbon quaternary stereogenic centers through catalytic asymmetric ring-closing metathesis.Journal of the American Chemical Society, vol. 128, no. 15, Apr. 2006, pp. 5153–57. Epmc, doi:10.1021/ja058428r.
Lee A-L, Malcolmson SJ, Puglisi A, Schrock RR, Hoveyda AH. Enantioselective synthesis of cyclic enol ethers and all-carbon quaternary stereogenic centers through catalytic asymmetric ring-closing metathesis. Journal of the American Chemical Society. 2006 Apr;128(15):5153–5157.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

April 2006

Volume

128

Issue

15

Start / End Page

5153 / 5157

Related Subject Headings

  • Stereoisomerism
  • Models, Molecular
  • General Chemistry
  • Ethers, Cyclic
  • Cycloparaffins
  • Cyclization
  • Catalysis
  • Alkenes
  • 40 Engineering
  • 34 Chemical sciences