New Directing Groups for Metal-Catalyzed Asymmetric Carbon–Carbon Bond-Forming Processes: Stereoconvergent Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles
The ability of two common protected forms of amines (carbamates and sulfonamides) to serve as directing groups in Ni-catalyzed Suzuki reactions has been exploited in the development of catalytic asymmetric methods for cross-coupling unactivated alkyl electrophiles. Racemic secondary bromides and chl...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2013
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| Online Access: | http://hdl.handle.net/1721.1/82051 |
| _version_ | 1811097418074161152 |
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| author | Wilsily, Ashraf Tramutola, Francesco Owston, Nathan A. Fu, Gregory C. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Wilsily, Ashraf Tramutola, Francesco Owston, Nathan A. Fu, Gregory C. |
| author_sort | Wilsily, Ashraf |
| collection | MIT |
| description | The ability of two common protected forms of amines (carbamates and sulfonamides) to serve as directing groups in Ni-catalyzed Suzuki reactions has been exploited in the development of catalytic asymmetric methods for cross-coupling unactivated alkyl electrophiles. Racemic secondary bromides and chlorides undergo C–C bond formation in a stereoconvergent process in good ee at room temperature in the presence of a commercially available Ni complex and chiral ligand. Structure–enantioselectivity studies designed to elucidate the site of binding to Ni (the oxygen of the carbamate and of the sulfonamide) led to the discovery that sulfones also serve as useful directing groups for asymmetric Suzuki cross-couplings of racemic alkyl halides. To our knowledge, this investigation provides the first examples of the use of sulfonamides or sulfones as effective directing groups in metal-catalyzed asymmetric C–C bond-forming reactions. A mechanistic study established that transmetalation occurs with retention of stereochemistry and that the resulting Ni–C bond does not undergo homolysis in subsequent stages of the catalytic cycle. |
| first_indexed | 2024-09-23T16:59:12Z |
| format | Article |
| id | mit-1721.1/82051 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:59:12Z |
| publishDate | 2013 |
| publisher | American Chemical Society (ACS) |
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| spelling | mit-1721.1/820512022-09-29T22:50:23Z New Directing Groups for Metal-Catalyzed Asymmetric Carbon–Carbon Bond-Forming Processes: Stereoconvergent Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles Wilsily, Ashraf Tramutola, Francesco Owston, Nathan A. Fu, Gregory C. Massachusetts Institute of Technology. Department of Chemistry Wilsily, Ashraf Tramutola, Francesco Owston, Nathan A. Fu, Gregory C. The ability of two common protected forms of amines (carbamates and sulfonamides) to serve as directing groups in Ni-catalyzed Suzuki reactions has been exploited in the development of catalytic asymmetric methods for cross-coupling unactivated alkyl electrophiles. Racemic secondary bromides and chlorides undergo C–C bond formation in a stereoconvergent process in good ee at room temperature in the presence of a commercially available Ni complex and chiral ligand. Structure–enantioselectivity studies designed to elucidate the site of binding to Ni (the oxygen of the carbamate and of the sulfonamide) led to the discovery that sulfones also serve as useful directing groups for asymmetric Suzuki cross-couplings of racemic alkyl halides. To our knowledge, this investigation provides the first examples of the use of sulfonamides or sulfones as effective directing groups in metal-catalyzed asymmetric C–C bond-forming reactions. A mechanistic study established that transmetalation occurs with retention of stereochemistry and that the resulting Ni–C bond does not undergo homolysis in subsequent stages of the catalytic cycle. National Institute of General Medical Sciences (U.S.) (Grant R01-GM62871) 2013-11-08T17:52:16Z 2013-11-08T17:52:16Z 2012-03 2012-02 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/82051 Wilsily, Ashraf, Francesco Tramutola, Nathan A. Owston, and Gregory C. Fu. “New Directing Groups for Metal-Catalyzed Asymmetric Carbon–Carbon Bond-Forming Processes: Stereoconvergent Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles.” Journal of the American Chemical Society 134, no. 13 (April 4, 2012): 5794-5797. en_US http://dx.doi.org/10.1021/ja301612y 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 (ACS) PMC |
| spellingShingle | Wilsily, Ashraf Tramutola, Francesco Owston, Nathan A. Fu, Gregory C. New Directing Groups for Metal-Catalyzed Asymmetric Carbon–Carbon Bond-Forming Processes: Stereoconvergent Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles |
| title | New Directing Groups for Metal-Catalyzed Asymmetric Carbon–Carbon Bond-Forming Processes: Stereoconvergent Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles |
| title_full | New Directing Groups for Metal-Catalyzed Asymmetric Carbon–Carbon Bond-Forming Processes: Stereoconvergent Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles |
| title_fullStr | New Directing Groups for Metal-Catalyzed Asymmetric Carbon–Carbon Bond-Forming Processes: Stereoconvergent Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles |
| title_full_unstemmed | New Directing Groups for Metal-Catalyzed Asymmetric Carbon–Carbon Bond-Forming Processes: Stereoconvergent Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles |
| title_short | New Directing Groups for Metal-Catalyzed Asymmetric Carbon–Carbon Bond-Forming Processes: Stereoconvergent Alkyl–Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles |
| title_sort | new directing groups for metal catalyzed asymmetric carbon carbon bond forming processes stereoconvergent alkyl alkyl suzuki cross couplings of unactivated electrophiles |
| url | http://hdl.handle.net/1721.1/82051 |
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