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Biphenyl-Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes

Ziegler, Daniel T. and Riesgo, Lorena and Ikeda, Takuya and Fujiwara, Yuji and Fu, Gregory C. (2014) Biphenyl-Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes. Angewandte Chemie International Edition, 53 (48). pp. 13183-13187. ISSN 1433-7851. PMCID PMC4433032. http://resolver.caltech.edu/CaltechAUTHORS:20141015-153508295

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Abstract

Because of the frequent occurrence of cyclopentane subunits in bioactive compounds, the development of efficient catalytic asymmetric methods for their synthesis is an important objective. Introduced herein is a new family of chiral nucleophilic catalysts, biphenyl-derived phosphepines, and we apply them to an enantioselective variant of a useful [4+1] annulation. A range of one-carbon coupling partners can be employed, thereby generating cyclopentenes which bear a fully substituted stereocenter [either all-carbon or heteroatom-substituted (sulfur and phosphorus)]. Stereocenters at the other four positions of the cyclopentane ring can also be introduced with good stereoselectivity. An initial mechanistic study indicates that phosphine addition to the electrophilic four-carbon coupling partner is not the turnover-limiting step of the catalytic cycle.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://onlinelibrary.wiley.com/doi/10.1002/anie.201405854/abstractPublisherArticle
http://dx.doi.org/10.1002/anie.201405854DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/anie.201405854/suppinfoPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4433032/PubMed CentralArticle
ORCID:
AuthorORCID
Fu, Gregory C.0000-0002-0927-680X
Additional Information:© 2014 Wiley-VCH Verlag GmbH & Co. Received: June 2, 2014. Revised: July 15, 2014. Article first published online: 6 Oct 2014. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM57034), EMD Serono (fellowship support for D.T.Z.), the Spanish MICINN (fellowship support for L.R.), Daiichi Sankyo Co., Ltd (fellowship support for T.I.), and Dainippon Sumitomo Pharma Co., Ltd. (fellowship support for Y.F.). We thank Trixia Buscagan, Dr. Søren Kramer, Dr. Allen Oliver (University of Notre Dame), Dr. Nathan D. Schley, Dr. Michael K. Takase, Dr. David VanderVelde, Dr. Scott C. Virgil, and Dr. Ashraf Wilsily for assistance and for helpful discussions.
Funders:
Funding AgencyGrant Number
NIHR01-GM57034
EMD SeronoUNSPECIFIED
MICINN Ministerio de Ciencia e Innovación (MICINN)UNSPECIFIED
Daiichi Sankyo Co., Ltd.UNSPECIFIED
Dainippon Sumitomo Pharma Co., Ltd.UNSPECIFIED
PubMed Central ID:PMC4433032
Record Number:CaltechAUTHORS:20141015-153508295
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20141015-153508295
Official Citation:Ziegler, D. T., Riesgo, L., Ikeda, T., Fujiwara, Y. and Fu, G. C. (2014), Biphenyl-Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes. Angew. Chem. Int. Ed., 53: 13183–13187. doi: 10.1002/anie.201405854
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:50426
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:15 Oct 2014 22:49
Last Modified:12 Dec 2016 21:20

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