Palladium(0)‐Catalyzed Anti‐Selective Addition‐Cyclizations of Alkynyl Electrophiles
Palladium(0)/monophosphine complexes catalyze anti‐selective alkylative, arylative, and alkynylative cyclizations of alkynyl electrophiles with organometallic reagents. The remarkable anti‐selectivity results from novel oxidative addition, that is, the nucleophilic attack of electron‐rich palladium(...
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| Veröffentlicht in: | Chemistry : a European journal 2023-01, Vol.29 (6), p.e202203068-n/a |
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| creator | Tsukamoto, Hirokazu Ito, Kazuya Ueno, Tatsuhiko Shiraishi, Mitsugu Kondo, Yoshinori Doi, Takayuki |
| description | Palladium(0)/monophosphine complexes catalyze anti‐selective alkylative, arylative, and alkynylative cyclizations of alkynyl electrophiles with organometallic reagents. The remarkable anti‐selectivity results from novel oxidative addition, that is, the nucleophilic attack of electron‐rich palladium(0) on the electrophile across the alkyne followed by transmetalation and reductive elimination (“anti‐Wacker”‐type cyclization). With regard to 5‐alkynals, triphenylphosphine (PPh3)‐ligated palladium(0) catalyzes the cyclization of terminal alkynes and conjugated alkenyl‐ or alkynyl‐substituted ones to afford 2‐cyclohexen‐1‐ol and 2‐alkylidene‐cyclopentanol derivatives, respectively. For 6‐alkyl‐ or 6‐aryl‐5‐alkynals, the cyclization does not proceed with the palladium/PPh3 catalyst; however, it does proceed with palladium/tricyclohexylphosphine (PCy3), to yield the former products predominantly. Remarkably, the latter catalyst completely switches the regioselectivity in the cyclization of the conjugated diyne‐aldehydes. Notably, palladium/PPh3‐catalyzed cyclizations also proceed with other organometallics or even without them.
Palladium(0)/monophosphine complexes catalyze anti‐selective arylative cyclizations of alkynyl electrophiles with organometallic reagents. Remarkably, the regioselectivity in the cyclization of conjugated diyne‐aldehydes can be controlled by a choice of the phosphine ligand, with triphenylphosphine and tricyclohexylphosphine leading to the exclusive formation of 2‐alkylidene‐cyclopentanol and 2‐cyclohexen‐1‐ol derivatives, respectively. |
| doi_str_mv | 10.1002/chem.202203068 |
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Palladium(0)/monophosphine complexes catalyze anti‐selective arylative cyclizations of alkynyl electrophiles with organometallic reagents. Remarkably, the regioselectivity in the cyclization of conjugated diyne‐aldehydes can be controlled by a choice of the phosphine ligand, with triphenylphosphine and tricyclohexylphosphine leading to the exclusive formation of 2‐alkylidene‐cyclopentanol and 2‐cyclohexen‐1‐ol derivatives, respectively.</description><identifier>ISSN: 0947-6539</identifier><identifier>ISSN: 1521-3765</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.202203068</identifier><identifier>PMID: 36333971</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Aldehydes ; Alkylation ; Alkylidene ; Alkynes ; anti-selective cyclization ; Catalysts ; Chemistry ; conjugated alkyne ; Organometallic compounds ; oxidative addition ; Palladium ; phosphine ; Reagents ; Regioselectivity ; Selectivity ; Switches</subject><ispartof>Chemistry : a European journal, 2023-01, Vol.29 (6), p.e202203068-n/a</ispartof><rights>2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH</rights><rights>2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.</rights><rights>2022. This article is published under http://creativecommons.org/licenses/by-nc-nd/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-c4298-6808d8be383b3d0863ed92f81709aba040639683bf747e6fcda449f1abecd18f3</citedby><cites>FETCH-LOGICAL-c4298-6808d8be383b3d0863ed92f81709aba040639683bf747e6fcda449f1abecd18f3</cites><orcidid>0000-0002-7849-6427</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.202203068$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.202203068$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>230,314,776,780,881,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/36333971$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Tsukamoto, Hirokazu</creatorcontrib><creatorcontrib>Ito, Kazuya</creatorcontrib><creatorcontrib>Ueno, Tatsuhiko</creatorcontrib><creatorcontrib>Shiraishi, Mitsugu</creatorcontrib><creatorcontrib>Kondo, Yoshinori</creatorcontrib><creatorcontrib>Doi, Takayuki</creatorcontrib><title>Palladium(0)‐Catalyzed Anti‐Selective Addition‐Cyclizations of Alkynyl Electrophiles</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>Palladium(0)/monophosphine complexes catalyze anti‐selective alkylative, arylative, and alkynylative cyclizations of alkynyl electrophiles with organometallic reagents. The remarkable anti‐selectivity results from novel oxidative addition, that is, the nucleophilic attack of electron‐rich palladium(0) on the electrophile across the alkyne followed by transmetalation and reductive elimination (“anti‐Wacker”‐type cyclization). With regard to 5‐alkynals, triphenylphosphine (PPh3)‐ligated palladium(0) catalyzes the cyclization of terminal alkynes and conjugated alkenyl‐ or alkynyl‐substituted ones to afford 2‐cyclohexen‐1‐ol and 2‐alkylidene‐cyclopentanol derivatives, respectively. For 6‐alkyl‐ or 6‐aryl‐5‐alkynals, the cyclization does not proceed with the palladium/PPh3 catalyst; however, it does proceed with palladium/tricyclohexylphosphine (PCy3), to yield the former products predominantly. Remarkably, the latter catalyst completely switches the regioselectivity in the cyclization of the conjugated diyne‐aldehydes. Notably, palladium/PPh3‐catalyzed cyclizations also proceed with other organometallics or even without them.
Palladium(0)/monophosphine complexes catalyze anti‐selective arylative cyclizations of alkynyl electrophiles with organometallic reagents. Remarkably, the regioselectivity in the cyclization of conjugated diyne‐aldehydes can be controlled by a choice of the phosphine ligand, with triphenylphosphine and tricyclohexylphosphine leading to the exclusive formation of 2‐alkylidene‐cyclopentanol and 2‐cyclohexen‐1‐ol derivatives, respectively.</description><subject>Aldehydes</subject><subject>Alkylation</subject><subject>Alkylidene</subject><subject>Alkynes</subject><subject>anti-selective cyclization</subject><subject>Catalysts</subject><subject>Chemistry</subject><subject>conjugated alkyne</subject><subject>Organometallic compounds</subject><subject>oxidative addition</subject><subject>Palladium</subject><subject>phosphine</subject><subject>Reagents</subject><subject>Regioselectivity</subject><subject>Selectivity</subject><subject>Switches</subject><issn>0947-6539</issn><issn>1521-3765</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><recordid>eNqFkctu1DAUhi0EotPCliWKxKZdZDi2E19WaDQaaKUikIANG8uxHcbFSaZxUpSueASekSepoynDZcPqyD6fP_mcH6FnGJYYgLw0W9csCRACFJh4gBa4JDinnJUP0QJkwXNWUnmEjmO8AgDJKH2MjmgqVHK8QJ_f6xC09WNzCmc_v_9Y60GH6dbZbNUOPl18cMGZwd-4bGWtH3zXztRkgr_V8ylmXZ2twtepnUK2mdm-2219cPEJelTrEN3T-3qCPr3efFyf55fv3lysV5e5KYgUORMgrKgcFbSiFgSjzkpSC8xB6kpDAYxKlpo1L7hjtbG6KGSNdeWMxaKmJ-jV3rsbq8ZZ49qh10Htet_oflKd9urvTuu36kt3ozBgEBiXyXB6b-i769HFQTU-GpcW07pujIpwSkrKGJnRF_-gV93Yt2m-RHHKi5JLmajlnjJ9F2Pv6sNvMKg5NzXnpg65pQfP_5zhgP8KKgFyD3xLq53-o1Pr883b3_I7RZ2oiQ</recordid><startdate>20230127</startdate><enddate>20230127</enddate><creator>Tsukamoto, Hirokazu</creator><creator>Ito, Kazuya</creator><creator>Ueno, Tatsuhiko</creator><creator>Shiraishi, Mitsugu</creator><creator>Kondo, Yoshinori</creator><creator>Doi, Takayuki</creator><general>Wiley Subscription Services, Inc</general><general>John Wiley and Sons Inc</general><scope>24P</scope><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><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-7849-6427</orcidid></search><sort><creationdate>20230127</creationdate><title>Palladium(0)‐Catalyzed Anti‐Selective Addition‐Cyclizations of Alkynyl Electrophiles</title><author>Tsukamoto, Hirokazu ; Ito, Kazuya ; Ueno, Tatsuhiko ; Shiraishi, Mitsugu ; Kondo, Yoshinori ; Doi, Takayuki</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4298-6808d8be383b3d0863ed92f81709aba040639683bf747e6fcda449f1abecd18f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Aldehydes</topic><topic>Alkylation</topic><topic>Alkylidene</topic><topic>Alkynes</topic><topic>anti-selective cyclization</topic><topic>Catalysts</topic><topic>Chemistry</topic><topic>conjugated alkyne</topic><topic>Organometallic compounds</topic><topic>oxidative addition</topic><topic>Palladium</topic><topic>phosphine</topic><topic>Reagents</topic><topic>Regioselectivity</topic><topic>Selectivity</topic><topic>Switches</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tsukamoto, Hirokazu</creatorcontrib><creatorcontrib>Ito, Kazuya</creatorcontrib><creatorcontrib>Ueno, Tatsuhiko</creatorcontrib><creatorcontrib>Shiraishi, Mitsugu</creatorcontrib><creatorcontrib>Kondo, Yoshinori</creatorcontrib><creatorcontrib>Doi, Takayuki</creatorcontrib><collection>Wiley Online Library Open Access</collection><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><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tsukamoto, Hirokazu</au><au>Ito, Kazuya</au><au>Ueno, Tatsuhiko</au><au>Shiraishi, Mitsugu</au><au>Kondo, Yoshinori</au><au>Doi, Takayuki</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Palladium(0)‐Catalyzed Anti‐Selective Addition‐Cyclizations of Alkynyl Electrophiles</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2023-01-27</date><risdate>2023</risdate><volume>29</volume><issue>6</issue><spage>e202203068</spage><epage>n/a</epage><pages>e202203068-n/a</pages><issn>0947-6539</issn><issn>1521-3765</issn><eissn>1521-3765</eissn><abstract>Palladium(0)/monophosphine complexes catalyze anti‐selective alkylative, arylative, and alkynylative cyclizations of alkynyl electrophiles with organometallic reagents. The remarkable anti‐selectivity results from novel oxidative addition, that is, the nucleophilic attack of electron‐rich palladium(0) on the electrophile across the alkyne followed by transmetalation and reductive elimination (“anti‐Wacker”‐type cyclization). With regard to 5‐alkynals, triphenylphosphine (PPh3)‐ligated palladium(0) catalyzes the cyclization of terminal alkynes and conjugated alkenyl‐ or alkynyl‐substituted ones to afford 2‐cyclohexen‐1‐ol and 2‐alkylidene‐cyclopentanol derivatives, respectively. For 6‐alkyl‐ or 6‐aryl‐5‐alkynals, the cyclization does not proceed with the palladium/PPh3 catalyst; however, it does proceed with palladium/tricyclohexylphosphine (PCy3), to yield the former products predominantly. Remarkably, the latter catalyst completely switches the regioselectivity in the cyclization of the conjugated diyne‐aldehydes. Notably, palladium/PPh3‐catalyzed cyclizations also proceed with other organometallics or even without them.
Palladium(0)/monophosphine complexes catalyze anti‐selective arylative cyclizations of alkynyl electrophiles with organometallic reagents. Remarkably, the regioselectivity in the cyclization of conjugated diyne‐aldehydes can be controlled by a choice of the phosphine ligand, with triphenylphosphine and tricyclohexylphosphine leading to the exclusive formation of 2‐alkylidene‐cyclopentanol and 2‐cyclohexen‐1‐ol derivatives, respectively.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>36333971</pmid><doi>10.1002/chem.202203068</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0002-7849-6427</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Aldehydes Alkylation Alkylidene Alkynes anti-selective cyclization Catalysts Chemistry conjugated alkyne Organometallic compounds oxidative addition Palladium phosphine Reagents Regioselectivity Selectivity Switches |
| title | Palladium(0)‐Catalyzed Anti‐Selective Addition‐Cyclizations of Alkynyl Electrophiles |
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