Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates
Copper‐catalyzed stereoconvergent allylation of chiral sp3‐hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper‐catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)dib...
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| Veröffentlicht in: | Chemistry : a European journal 2020-02, Vol.26 (12), p.2592-2596 |
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| creator | Han, Jung Tae Kim, Seoung‐Tae Baik, Mu‐Hyun Yun, Jaesook |
| description | Copper‐catalyzed stereoconvergent allylation of chiral sp3‐hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper‐catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)diboron, and racemic allylic phosphates provided β‐chiral alkylboronates possessing (E)‐alkenyl moiety through a direct stereoconvergent allylic coupling with concomitant generation of a C(sp3)‐stereogenic center. A range of vinyl (hetero)arenes and secondary allylic phosphates bearing 1°, 2°, 3° alkyl and phenyl α‐substituents were suitable for the reaction, forming products with high enantioselectivities up to 95 % ee. Density functional theory calculations were conducted in detail to elucidate the origin of the observed regioselectivity of borylcupration and stereoconvergent (E)‐olefin formation from racemic allylic phosphates.
Direct stereoconvergent coupling of chiral alkylcopper species with racemic allylic phosphates was developed. Mechanistic studies and DFT calculations explain the origin of direct stereoconvergence in the tandem coupling process. |
| doi_str_mv | 10.1002/chem.201905361 |
| format | Article |
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Direct stereoconvergent coupling of chiral alkylcopper species with racemic allylic phosphates was developed. Mechanistic studies and DFT calculations explain the origin of direct stereoconvergence in the tandem coupling process.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201905361</identifier><identifier>PMID: 31788874</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>AC generators ; Allyl compounds ; Aromatic compounds ; asymmetric allylation ; Catalysts ; Chemical reactions ; Chemistry ; Copper ; Coupling ; Density functional theory ; enantioselectivity ; homogeneous catalysis ; Nucleophiles ; Phosphates ; Regioselectivity ; substitution</subject><ispartof>Chemistry : a European journal, 2020-02, Vol.26 (12), p.2592-2596</ispartof><rights>2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2020 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4101-9f4a770c8693680bba9ee736fec0ddf701f6c561387fa0801f415afe77e7f8fd3</citedby><cites>FETCH-LOGICAL-c4101-9f4a770c8693680bba9ee736fec0ddf701f6c561387fa0801f415afe77e7f8fd3</cites><orcidid>0000-0003-4380-7878</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%2Fchem.201905361$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201905361$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1416,27923,27924,45573,45574</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31788874$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Han, Jung Tae</creatorcontrib><creatorcontrib>Kim, Seoung‐Tae</creatorcontrib><creatorcontrib>Baik, Mu‐Hyun</creatorcontrib><creatorcontrib>Yun, Jaesook</creatorcontrib><title>Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>Copper‐catalyzed stereoconvergent allylation of chiral sp3‐hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper‐catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)diboron, and racemic allylic phosphates provided β‐chiral alkylboronates possessing (E)‐alkenyl moiety through a direct stereoconvergent allylic coupling with concomitant generation of a C(sp3)‐stereogenic center. A range of vinyl (hetero)arenes and secondary allylic phosphates bearing 1°, 2°, 3° alkyl and phenyl α‐substituents were suitable for the reaction, forming products with high enantioselectivities up to 95 % ee. Density functional theory calculations were conducted in detail to elucidate the origin of the observed regioselectivity of borylcupration and stereoconvergent (E)‐olefin formation from racemic allylic phosphates.
Direct stereoconvergent coupling of chiral alkylcopper species with racemic allylic phosphates was developed. Mechanistic studies and DFT calculations explain the origin of direct stereoconvergence in the tandem coupling process.</description><subject>AC generators</subject><subject>Allyl compounds</subject><subject>Aromatic compounds</subject><subject>asymmetric allylation</subject><subject>Catalysts</subject><subject>Chemical reactions</subject><subject>Chemistry</subject><subject>Copper</subject><subject>Coupling</subject><subject>Density functional theory</subject><subject>enantioselectivity</subject><subject>homogeneous catalysis</subject><subject>Nucleophiles</subject><subject>Phosphates</subject><subject>Regioselectivity</subject><subject>substitution</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNqFkUtv2zAQhImgQew4vfZYCOilFzlLUSKpo-HmBeSFtD0LNL2s5FKiQkoJ_O9Dw3kAvfS02MU3g8UMIV8ozClAdqprbOcZ0BIKxukBmdIioykTvPhEplDmIuUFKyfkOIQNAJScsSMyYVRIKUU-Jfij8aiH5OeAHp123RP6P9gNycLarVVD47rEmWRZN17ZePy7tdr1PfrkdtQWXV83FkPy3Ax18qA0to3eS-O8r13oazVgOCGHRtmAn1_njPw-P_u1vEyv7y6ulovrVOcUaFqaXAkBWvKScQmrlSoRBeMGNazXRgA1XBecMimMAhnXnBbKoBAojDRrNiPf9769d48jhqFqm6DRWtWhG0OVsQw4k5AVEf32D7pxo-_id5HiPAfgYkfN95T2LgSPpup90yq_rShUuwKqXQHVewFR8PXVdly1uH7H3xKPQLkHnmNw2__YVcvLs5sP8xfmD5MR</recordid><startdate>20200226</startdate><enddate>20200226</enddate><creator>Han, Jung Tae</creator><creator>Kim, Seoung‐Tae</creator><creator>Baik, Mu‐Hyun</creator><creator>Yun, Jaesook</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-4380-7878</orcidid></search><sort><creationdate>20200226</creationdate><title>Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates</title><author>Han, Jung Tae ; Kim, Seoung‐Tae ; Baik, Mu‐Hyun ; Yun, Jaesook</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4101-9f4a770c8693680bba9ee736fec0ddf701f6c561387fa0801f415afe77e7f8fd3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>AC generators</topic><topic>Allyl compounds</topic><topic>Aromatic compounds</topic><topic>asymmetric allylation</topic><topic>Catalysts</topic><topic>Chemical reactions</topic><topic>Chemistry</topic><topic>Copper</topic><topic>Coupling</topic><topic>Density functional theory</topic><topic>enantioselectivity</topic><topic>homogeneous catalysis</topic><topic>Nucleophiles</topic><topic>Phosphates</topic><topic>Regioselectivity</topic><topic>substitution</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Han, Jung Tae</creatorcontrib><creatorcontrib>Kim, Seoung‐Tae</creatorcontrib><creatorcontrib>Baik, Mu‐Hyun</creatorcontrib><creatorcontrib>Yun, Jaesook</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Han, Jung Tae</au><au>Kim, Seoung‐Tae</au><au>Baik, Mu‐Hyun</au><au>Yun, Jaesook</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2020-02-26</date><risdate>2020</risdate><volume>26</volume><issue>12</issue><spage>2592</spage><epage>2596</epage><pages>2592-2596</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>Copper‐catalyzed stereoconvergent allylation of chiral sp3‐hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper‐catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)diboron, and racemic allylic phosphates provided β‐chiral alkylboronates possessing (E)‐alkenyl moiety through a direct stereoconvergent allylic coupling with concomitant generation of a C(sp3)‐stereogenic center. A range of vinyl (hetero)arenes and secondary allylic phosphates bearing 1°, 2°, 3° alkyl and phenyl α‐substituents were suitable for the reaction, forming products with high enantioselectivities up to 95 % ee. Density functional theory calculations were conducted in detail to elucidate the origin of the observed regioselectivity of borylcupration and stereoconvergent (E)‐olefin formation from racemic allylic phosphates.
Direct stereoconvergent coupling of chiral alkylcopper species with racemic allylic phosphates was developed. Mechanistic studies and DFT calculations explain the origin of direct stereoconvergence in the tandem coupling process.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>31788874</pmid><doi>10.1002/chem.201905361</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0003-4380-7878</orcidid></addata></record> |
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| subjects | AC generators Allyl compounds Aromatic compounds asymmetric allylation Catalysts Chemical reactions Chemistry Copper Coupling Density functional theory enantioselectivity homogeneous catalysis Nucleophiles Phosphates Regioselectivity substitution |
| title | Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates |
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