Enantio‐ and Regioconvergent Nickel‐Catalyzed C(sp3)−C(sp3) Cross‐Coupling of Allylic Electrophiles Steered by a Silyl Group
A two‐step sequence for the enantio‐ and diastereoselective synthesis of exclusively alkyl‐substituted acyclic allylic systems with a stereocenter in the allylic position is reported. The asymmetric induction and the site selectivity are controlled in an enantio‐ and regioconvergent nickel‐catalyzed...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2021-06, Vol.60 (24), p.13652-13655 |
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| creator | Kranidiotis‐Hisatomi, Nektarios Yi, Hong Oestreich, Martin |
| description | A two‐step sequence for the enantio‐ and diastereoselective synthesis of exclusively alkyl‐substituted acyclic allylic systems with a stereocenter in the allylic position is reported. The asymmetric induction and the site selectivity are controlled in an enantio‐ and regioconvergent nickel‐catalyzed C(sp3)−C(sp3) cross‐coupling of regioisomeric mixtures of racemic α‐/γ‐silylated allylic halides and primary alkylzinc reagents. The silyl group steers the allylic displacement towards the formation of the vinylsilane regioisomer, and the resulting C(sp2)−Si bond serves as a linchpin for the installation of various C(sp3) substituents in a subsequent step.
A nickel‐catalyzed cross‐coupling of regioisomeric mixtures of racemic silylated allylic halides and primary alkylzinc reagents enables the enantio‐ and regioconvergent synthesis of vinylsilanes with an allylic stereocenter. The silyl group controls the regiochemical outcome and is at the same time a placeholder for another alkyl substituent that can be installed in a subsequent cross‐coupling. |
| doi_str_mv | 10.1002/anie.202102233 |
| format | Article |
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A nickel‐catalyzed cross‐coupling of regioisomeric mixtures of racemic silylated allylic halides and primary alkylzinc reagents enables the enantio‐ and regioconvergent synthesis of vinylsilanes with an allylic stereocenter. The silyl group controls the regiochemical outcome and is at the same time a placeholder for another alkyl substituent that can be installed in a subsequent cross‐coupling.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202102233</identifier><identifier>PMID: 33822445</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Communication ; Communications ; Cross coupling ; Halides ; Nickel ; radical reactions ; Reagents ; Selectivity ; silicon ; Stereoselectivity ; synthetic methods</subject><ispartof>Angewandte Chemie International Edition, 2021-06, Vol.60 (24), p.13652-13655</ispartof><rights>2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH</rights><rights>2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.</rights><rights>2021. This article is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5053-2f71f7a1d395ec42175e385a52a7a965f2a8c17633a08be5926d37af0e4223f3</citedby><cites>FETCH-LOGICAL-c5053-2f71f7a1d395ec42175e385a52a7a965f2a8c17633a08be5926d37af0e4223f3</cites><orcidid>0000-0002-3337-1452 ; 0000-0002-1487-9218 ; 0000-0002-8267-1099</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.202102233$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202102233$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>230,314,780,784,885,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/33822445$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kranidiotis‐Hisatomi, Nektarios</creatorcontrib><creatorcontrib>Yi, Hong</creatorcontrib><creatorcontrib>Oestreich, Martin</creatorcontrib><title>Enantio‐ and Regioconvergent Nickel‐Catalyzed C(sp3)−C(sp3) Cross‐Coupling of Allylic Electrophiles Steered by a Silyl Group</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>A two‐step sequence for the enantio‐ and diastereoselective synthesis of exclusively alkyl‐substituted acyclic allylic systems with a stereocenter in the allylic position is reported. The asymmetric induction and the site selectivity are controlled in an enantio‐ and regioconvergent nickel‐catalyzed C(sp3)−C(sp3) cross‐coupling of regioisomeric mixtures of racemic α‐/γ‐silylated allylic halides and primary alkylzinc reagents. The silyl group steers the allylic displacement towards the formation of the vinylsilane regioisomer, and the resulting C(sp2)−Si bond serves as a linchpin for the installation of various C(sp3) substituents in a subsequent step.
A nickel‐catalyzed cross‐coupling of regioisomeric mixtures of racemic silylated allylic halides and primary alkylzinc reagents enables the enantio‐ and regioconvergent synthesis of vinylsilanes with an allylic stereocenter. The silyl group controls the regiochemical outcome and is at the same time a placeholder for another alkyl substituent that can be installed in a subsequent cross‐coupling.</description><subject>Communication</subject><subject>Communications</subject><subject>Cross coupling</subject><subject>Halides</subject><subject>Nickel</subject><subject>radical reactions</subject><subject>Reagents</subject><subject>Selectivity</subject><subject>silicon</subject><subject>Stereoselectivity</subject><subject>synthetic methods</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkTtvFDEUhS0EImGhpUSWaJJiFj_Hsw3SarQJkaIgkfSW1-PZOHjtwZ5JNFQUFJSIn5hfgkcblkdD5Svd7x7few4ALzGaY4TIG-WtmRNEMCKE0kfgEHOCCyoEfZxrRmkhKo4PwLOUbjJfVah8Cg4orQhhjB-CryuvfG_D_ZfvUPkGfjAbG3TwtyZujO_hhdUfjcvdWvXKjZ9NA-uj1NHj-28_dgWsY0hpIsLQOes3MLRw6dzorIYrZ3QfQ3dtnUnwsjcmZoX1CBW8tBmBpzFPPQdPWuWSefHwzsDVyeqqflecvz89q5fnheaI04K0ArdC4YYuuNGMYMENrbjiRAm1KHlLVKWxKClVqFobviBlQ4VqkWHZnJbOwNudbDest6bR-b6onOyi3ao4yqCs_Lvj7bXchFtZEY5FNnMGjh4EYvg0mNTLrU3aOKe8CUOShKP8p2Csyujrf9CbMESfr8sU5axkTEzUfEfpycNo2v0yGMkpXznlK_f55oFXf56wx38FmoHFDrjLjo__kZPLi7PVb_GfQIa1_g</recordid><startdate>20210607</startdate><enddate>20210607</enddate><creator>Kranidiotis‐Hisatomi, Nektarios</creator><creator>Yi, Hong</creator><creator>Oestreich, Martin</creator><general>Wiley Subscription Services, Inc</general><general>John Wiley and Sons Inc</general><scope>24P</scope><scope>WIN</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-3337-1452</orcidid><orcidid>https://orcid.org/0000-0002-1487-9218</orcidid><orcidid>https://orcid.org/0000-0002-8267-1099</orcidid></search><sort><creationdate>20210607</creationdate><title>Enantio‐ and Regioconvergent Nickel‐Catalyzed C(sp3)−C(sp3) Cross‐Coupling of Allylic Electrophiles Steered by a Silyl Group</title><author>Kranidiotis‐Hisatomi, Nektarios ; Yi, Hong ; Oestreich, Martin</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5053-2f71f7a1d395ec42175e385a52a7a965f2a8c17633a08be5926d37af0e4223f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Communication</topic><topic>Communications</topic><topic>Cross coupling</topic><topic>Halides</topic><topic>Nickel</topic><topic>radical reactions</topic><topic>Reagents</topic><topic>Selectivity</topic><topic>silicon</topic><topic>Stereoselectivity</topic><topic>synthetic methods</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kranidiotis‐Hisatomi, Nektarios</creatorcontrib><creatorcontrib>Yi, Hong</creatorcontrib><creatorcontrib>Oestreich, Martin</creatorcontrib><collection>Wiley Online Library Open Access</collection><collection>Wiley Online Library Free Content</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kranidiotis‐Hisatomi, Nektarios</au><au>Yi, Hong</au><au>Oestreich, Martin</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Enantio‐ and Regioconvergent Nickel‐Catalyzed C(sp3)−C(sp3) Cross‐Coupling of Allylic Electrophiles Steered by a Silyl Group</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2021-06-07</date><risdate>2021</risdate><volume>60</volume><issue>24</issue><spage>13652</spage><epage>13655</epage><pages>13652-13655</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>A two‐step sequence for the enantio‐ and diastereoselective synthesis of exclusively alkyl‐substituted acyclic allylic systems with a stereocenter in the allylic position is reported. 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A nickel‐catalyzed cross‐coupling of regioisomeric mixtures of racemic silylated allylic halides and primary alkylzinc reagents enables the enantio‐ and regioconvergent synthesis of vinylsilanes with an allylic stereocenter. The silyl group controls the regiochemical outcome and is at the same time a placeholder for another alkyl substituent that can be installed in a subsequent cross‐coupling.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>33822445</pmid><doi>10.1002/anie.202102233</doi><tpages>4</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-3337-1452</orcidid><orcidid>https://orcid.org/0000-0002-1487-9218</orcidid><orcidid>https://orcid.org/0000-0002-8267-1099</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Communication Communications Cross coupling Halides Nickel radical reactions Reagents Selectivity silicon Stereoselectivity synthetic methods |
| title | Enantio‐ and Regioconvergent Nickel‐Catalyzed C(sp3)−C(sp3) Cross‐Coupling of Allylic Electrophiles Steered by a Silyl Group |
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