Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters
- Creators
- Fujiwara, Yuji
-
Fu, Gregory C.
Abstract
Through the design and synthesis of a new chiral phosphepine, the first catalytic asymmetric method for the [3 + 2] cycloaddition of allenes with olefins has been developed that generates cyclopentenes that bear nitrogen-, phosphorus-, oxygen-, and sulfur-substituted quaternary stereocenters. A wide array of racemic γ-substituted allenes can be employed in this stereoconvergent process, which occurs with good enantioselectivity, diastereoselectivity, regioselectivity, and yield. Mechanistic studies, including a unique observation of a (modest) kinetic resolution of a racemic allene, are consistent with addition of the phosphepine to the allene being the turnover-limiting step of the catalytic cycle.
Additional Information
© 2011 American Chemical Society. Received: May 27, 2011. Published: July 18, 2011. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM57034) and Dainippon Sumitomo Pharma Co., Ltd. (fellowship for Y.F.). We thank Dr. Jonathan E. Wilson for a preliminary study.Attached Files
Accepted Version - nihms312878.pdf
Supplemental Material - ja2049012_si_001.pdf
Supplemental Material - ja2049012_si_002.cif
Supplemental Material - ja2049012_si_003.cif
Supplemental Material - ja2049012_si_004.cif
Supplemental Material - ja2049012_si_005.cif
Supplemental Material - ja2049012_si_006.cif
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Additional details
- PMCID
- PMC3150361
- Eprint ID
- 102853
- DOI
- 10.1021/ja2049012
- Resolver ID
- CaltechAUTHORS:20200428-095145770
- NIH
- R01-GM57034
- Dainippon Sumitomo Pharma Co., Ltd.
- Created
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2020-04-29Created from EPrint's datestamp field
- Updated
-
2021-11-16Created from EPrint's last_modified field