Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles
As part of our ongoing effort to expand the scope of cross-coupling reactions of alkyl electrophiles, we have pursued a strategy wherein the nucleophilic coupling partner includes a pendant olefin; after transmetalation by such a substrate, if β-migratory insertion proceeds faster than direct cross-...
| Main Authors: | , |
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2015
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| Online Access: | http://hdl.handle.net/1721.1/96696 |
| _version_ | 1811091146540056576 |
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| author | Cong, Huan Fu, Gregory C. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Cong, Huan Fu, Gregory C. |
| author_sort | Cong, Huan |
| collection | MIT |
| description | As part of our ongoing effort to expand the scope of cross-coupling reactions of alkyl electrophiles, we have pursued a strategy wherein the nucleophilic coupling partner includes a pendant olefin; after transmetalation by such a substrate, if β-migratory insertion proceeds faster than direct cross-coupling, an additional carbon–carbon bond and stereocenter can be formed. With the aid of a nickel/diamine catalyst (both components are commercially available), we have established the viability of this approach for the catalytic asymmetric synthesis of 2,3-dihydrobenzofurans and indanes. Furthermore, we have applied this new method to the construction of the dihydrobenzofuran core of fasiglifam, as well as to a cross-coupling with a racemic alkyl electrophile; in the latter process, the chiral catalyst controls two stereocenters, one that is newly generated in a β-migratory insertion and one that begins as a mixture of enantiomers. |
| first_indexed | 2024-09-23T14:57:44Z |
| format | Article |
| id | mit-1721.1/96696 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T14:57:44Z |
| publishDate | 2015 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/966962022-10-01T23:35:40Z Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles Cong, Huan Fu, Gregory C. Massachusetts Institute of Technology. Department of Chemistry Cong, Huan Fu, Gregory C. As part of our ongoing effort to expand the scope of cross-coupling reactions of alkyl electrophiles, we have pursued a strategy wherein the nucleophilic coupling partner includes a pendant olefin; after transmetalation by such a substrate, if β-migratory insertion proceeds faster than direct cross-coupling, an additional carbon–carbon bond and stereocenter can be formed. With the aid of a nickel/diamine catalyst (both components are commercially available), we have established the viability of this approach for the catalytic asymmetric synthesis of 2,3-dihydrobenzofurans and indanes. Furthermore, we have applied this new method to the construction of the dihydrobenzofuran core of fasiglifam, as well as to a cross-coupling with a racemic alkyl electrophile; in the latter process, the chiral catalyst controls two stereocenters, one that is newly generated in a β-migratory insertion and one that begins as a mixture of enantiomers. Gordon and Betty Moore Foundation National Institute of General Medical Sciences (U.S.) (R01-GM62871) 2015-04-22T15:49:00Z 2015-04-22T15:49:00Z 2014-03 2014-01 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/96696 Cong, Huan, and Gregory C. Fu. “Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles.” Journal of the American Chemical Society 136, no. 10 (March 12, 2014): 3788–3791. © 2014 American Chemical Society. en_US http://dx.doi.org/10.1021/ja500706v 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) American Chemical Society |
| spellingShingle | Cong, Huan Fu, Gregory C. Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles |
| title | Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles |
| title_full | Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles |
| title_fullStr | Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles |
| title_full_unstemmed | Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles |
| title_short | Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles |
| title_sort | catalytic enantioselective cyclization cross coupling with alkyl electrophiles |
| url | http://hdl.handle.net/1721.1/96696 |
| work_keys_str_mv | AT conghuan catalyticenantioselectivecyclizationcrosscouplingwithalkylelectrophiles AT fugregoryc catalyticenantioselectivecyclizationcrosscouplingwithalkylelectrophiles |