Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters
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...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society
2013
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| Online Access: | http://hdl.handle.net/1721.1/82012 |
| _version_ | 1826216295350140928 |
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| author | Fujiwara, Yuji Fu, Gregory C. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Fujiwara, Yuji Fu, Gregory C. |
| author_sort | Fujiwara, Yuji |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T16:45:25Z |
| format | Article |
| id | mit-1721.1/82012 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:45:25Z |
| publishDate | 2013 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/820122022-10-03T08:03:49Z Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters Fujiwara, Yuji Fu, Gregory C. Massachusetts Institute of Technology. Department of Chemistry Fu, Gregory C. Fujiwara, Yuji 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. National Institute of General Medical Sciences (U.S.) (grant R01-GM57034) Dainippon Pharmaceutical Co., Ltd. (Fellowship) 2013-11-06T21:27:25Z 2013-11-06T21:27:25Z 2011-08 2011-05 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/82012 Fujiwara, Yuji, and Gregory C. Fu. “Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters.” Journal of the American Chemical Society 133, no. 31 (August 10, 2011): 12293-12297. en_US http://dx.doi.org/10.1021/ja2049012 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society PMC |
| spellingShingle | Fujiwara, Yuji Fu, Gregory C. Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters |
| title | Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters |
| title_full | Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters |
| title_fullStr | Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters |
| title_full_unstemmed | Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters |
| title_short | Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters |
| title_sort | application of a new chiral phosphepine to the catalytic asymmetric synthesis of highly functionalized cyclopentenes that bear an array of heteroatom substituted quaternary stereocenters |
| url | http://hdl.handle.net/1721.1/82012 |
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