Cobalt‐Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2‐Aryl Vinylcyclopropanes
A cobalt‐catalyzed asymmetric sequential hydroboration/isomerization/hydroboration of 2‐aryl vinylcyclopropanes was for the first time reported for the preparation of valuable chiral 1,5‐bis(boronates) in good yields with excellent enantioselectivity via asymmetric sequential isomerization/hydrobora...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2022-07, Vol.61 (30), p.n/a |
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| creator | Chen, Chenhui Wang, Hongliang Li, Tongtong Lu, Dongpo Li, Jiajing Zhang, Xie Hong, Xin Lu, Zhan |
| description | A cobalt‐catalyzed asymmetric sequential hydroboration/isomerization/hydroboration of 2‐aryl vinylcyclopropanes was for the first time reported for the preparation of valuable chiral 1,5‐bis(boronates) in good yields with excellent enantioselectivity via asymmetric sequential isomerization/hydroboration of a trisubstituted alkene intermediate. The reaction was carried out smoothly and this protocol was used for asymmetric syntheses of (−)‐preclamol in gram‐scale. The two primary C(sp3)−B bonds in chiral 1,5‐bis(boronates) could be distinguished in iterative Suzuki–Miyaura cross‐coupling reaction, delivering chiral 1,2,5‐triaryl alkanes with excellent enantioselectivity. Based on experimental and computational studies, a cobalt‐hydride species was proposed as the active intermediate in hydroboration, isomerization, and second hydroboration reactions.
Chiral 1,5‐bis(boronates) were synthesized via an enantioselective cobalt‐catalyzed sequential hydroboration/isomerization/hydroboration of vinylcyclopropanes through a trisubstituted alkene intermediate. These chiral 1,5‐bis(boronates) were further converted into chiral 1,2,5‐triaryl alkanes by an iterative Suzuki–Miyaura cross‐coupling reaction with aryl halides. |
| doi_str_mv | 10.1002/anie.202205619 |
| format | Article |
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Chiral 1,5‐bis(boronates) were synthesized via an enantioselective cobalt‐catalyzed sequential hydroboration/isomerization/hydroboration of vinylcyclopropanes through a trisubstituted alkene intermediate. These chiral 1,5‐bis(boronates) were further converted into chiral 1,2,5‐triaryl alkanes by an iterative Suzuki–Miyaura cross‐coupling reaction with aryl halides.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202205619</identifier><identifier>PMID: 35607762</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Alkanes ; Aromatic compounds ; Asymmetry ; Chemical reactions ; Chiral Boronates ; Cobalt ; Computer applications ; Cross coupling ; Enantiomers ; Hydroboration ; Isomerization ; Iterative Coupling ; Iterative methods ; Vinylcyclopropanes</subject><ispartof>Angewandte Chemie International Edition, 2022-07, Vol.61 (30), p.n/a</ispartof><rights>2022 Wiley‐VCH GmbH</rights><rights>2022 Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4069-c7cee5a0aa7451ae98be9e390964654d75b1612954298d18547c59229fbfa653</citedby><cites>FETCH-LOGICAL-c4069-c7cee5a0aa7451ae98be9e390964654d75b1612954298d18547c59229fbfa653</cites><orcidid>0000-0003-4717-2814 ; 0000-0002-3069-079X ; 0000-0001-9629-1743</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.202205619$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202205619$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/35607762$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Chen, Chenhui</creatorcontrib><creatorcontrib>Wang, Hongliang</creatorcontrib><creatorcontrib>Li, Tongtong</creatorcontrib><creatorcontrib>Lu, Dongpo</creatorcontrib><creatorcontrib>Li, Jiajing</creatorcontrib><creatorcontrib>Zhang, Xie</creatorcontrib><creatorcontrib>Hong, Xin</creatorcontrib><creatorcontrib>Lu, Zhan</creatorcontrib><title>Cobalt‐Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2‐Aryl Vinylcyclopropanes</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>A cobalt‐catalyzed asymmetric sequential hydroboration/isomerization/hydroboration of 2‐aryl vinylcyclopropanes was for the first time reported for the preparation of valuable chiral 1,5‐bis(boronates) in good yields with excellent enantioselectivity via asymmetric sequential isomerization/hydroboration of a trisubstituted alkene intermediate. The reaction was carried out smoothly and this protocol was used for asymmetric syntheses of (−)‐preclamol in gram‐scale. The two primary C(sp3)−B bonds in chiral 1,5‐bis(boronates) could be distinguished in iterative Suzuki–Miyaura cross‐coupling reaction, delivering chiral 1,2,5‐triaryl alkanes with excellent enantioselectivity. Based on experimental and computational studies, a cobalt‐hydride species was proposed as the active intermediate in hydroboration, isomerization, and second hydroboration reactions.
Chiral 1,5‐bis(boronates) were synthesized via an enantioselective cobalt‐catalyzed sequential hydroboration/isomerization/hydroboration of vinylcyclopropanes through a trisubstituted alkene intermediate. These chiral 1,5‐bis(boronates) were further converted into chiral 1,2,5‐triaryl alkanes by an iterative Suzuki–Miyaura cross‐coupling reaction with aryl halides.</description><subject>Alkanes</subject><subject>Aromatic compounds</subject><subject>Asymmetry</subject><subject>Chemical reactions</subject><subject>Chiral Boronates</subject><subject>Cobalt</subject><subject>Computer applications</subject><subject>Cross coupling</subject><subject>Enantiomers</subject><subject>Hydroboration</subject><subject>Isomerization</subject><subject>Iterative Coupling</subject><subject>Iterative methods</subject><subject>Vinylcyclopropanes</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNqFkMFOwyAYgInRuDm9ejRNPHcDWqAcm0bdkkUPLl4b2tKEhZYNupju5CP4jD6JLJ0znjwB4eP7wwfALYJTBCGeiVbJKYYYQ0IRPwNjRDAKI8aic7-PoyhkCUEjcOXc2vNJAuklGEWEQsYoHoNtZgqhu6-Pz0x0Qvd7WQWp65tGdlaVwavc7mTbKaGDeV9ZUxgrOmXa2cKZRlq1H05_7gJTB9gLU9vr4E21vS77UpuNNRvRSncNLmqhnbw5rhOwenxYZfNw-fK0yNJlWMaQ8rBkpZREQCFYTJCQPCkklxGHnMaUxBUjBaIIcxJjnlQoITErCceY10UtKIkm4H7Q-rn-D67L12ZnWz8xx9RbfAgfaQKmA1Va45yVdb6xqhG2zxHMD4HzQ-D8FNg_uDtqd0UjqxP-U9QDfADelZb9P7o8fV48_Mq_AZRxi1w</recordid><startdate>20220725</startdate><enddate>20220725</enddate><creator>Chen, Chenhui</creator><creator>Wang, Hongliang</creator><creator>Li, Tongtong</creator><creator>Lu, Dongpo</creator><creator>Li, Jiajing</creator><creator>Zhang, Xie</creator><creator>Hong, Xin</creator><creator>Lu, Zhan</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><orcidid>https://orcid.org/0000-0003-4717-2814</orcidid><orcidid>https://orcid.org/0000-0002-3069-079X</orcidid><orcidid>https://orcid.org/0000-0001-9629-1743</orcidid></search><sort><creationdate>20220725</creationdate><title>Cobalt‐Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2‐Aryl Vinylcyclopropanes</title><author>Chen, Chenhui ; Wang, Hongliang ; Li, Tongtong ; Lu, Dongpo ; Li, Jiajing ; Zhang, Xie ; Hong, Xin ; Lu, Zhan</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4069-c7cee5a0aa7451ae98be9e390964654d75b1612954298d18547c59229fbfa653</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Alkanes</topic><topic>Aromatic compounds</topic><topic>Asymmetry</topic><topic>Chemical reactions</topic><topic>Chiral Boronates</topic><topic>Cobalt</topic><topic>Computer applications</topic><topic>Cross coupling</topic><topic>Enantiomers</topic><topic>Hydroboration</topic><topic>Isomerization</topic><topic>Iterative Coupling</topic><topic>Iterative methods</topic><topic>Vinylcyclopropanes</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Chen, Chenhui</creatorcontrib><creatorcontrib>Wang, Hongliang</creatorcontrib><creatorcontrib>Li, Tongtong</creatorcontrib><creatorcontrib>Lu, Dongpo</creatorcontrib><creatorcontrib>Li, Jiajing</creatorcontrib><creatorcontrib>Zhang, Xie</creatorcontrib><creatorcontrib>Hong, Xin</creatorcontrib><creatorcontrib>Lu, Zhan</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Chen, Chenhui</au><au>Wang, Hongliang</au><au>Li, Tongtong</au><au>Lu, Dongpo</au><au>Li, Jiajing</au><au>Zhang, Xie</au><au>Hong, Xin</au><au>Lu, Zhan</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Cobalt‐Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2‐Aryl Vinylcyclopropanes</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2022-07-25</date><risdate>2022</risdate><volume>61</volume><issue>30</issue><epage>n/a</epage><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>A cobalt‐catalyzed asymmetric sequential hydroboration/isomerization/hydroboration of 2‐aryl vinylcyclopropanes was for the first time reported for the preparation of valuable chiral 1,5‐bis(boronates) in good yields with excellent enantioselectivity via asymmetric sequential isomerization/hydroboration of a trisubstituted alkene intermediate. The reaction was carried out smoothly and this protocol was used for asymmetric syntheses of (−)‐preclamol in gram‐scale. The two primary C(sp3)−B bonds in chiral 1,5‐bis(boronates) could be distinguished in iterative Suzuki–Miyaura cross‐coupling reaction, delivering chiral 1,2,5‐triaryl alkanes with excellent enantioselectivity. Based on experimental and computational studies, a cobalt‐hydride species was proposed as the active intermediate in hydroboration, isomerization, and second hydroboration reactions.
Chiral 1,5‐bis(boronates) were synthesized via an enantioselective cobalt‐catalyzed sequential hydroboration/isomerization/hydroboration of vinylcyclopropanes through a trisubstituted alkene intermediate. These chiral 1,5‐bis(boronates) were further converted into chiral 1,2,5‐triaryl alkanes by an iterative Suzuki–Miyaura cross‐coupling reaction with aryl halides.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>35607762</pmid><doi>10.1002/anie.202205619</doi><tpages>8</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0003-4717-2814</orcidid><orcidid>https://orcid.org/0000-0002-3069-079X</orcidid><orcidid>https://orcid.org/0000-0001-9629-1743</orcidid></addata></record> |
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| subjects | Alkanes Aromatic compounds Asymmetry Chemical reactions Chiral Boronates Cobalt Computer applications Cross coupling Enantiomers Hydroboration Isomerization Iterative Coupling Iterative methods Vinylcyclopropanes |
| title | Cobalt‐Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2‐Aryl Vinylcyclopropanes |
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