Rhodium‐NHC‐Catalyzed gem‐Specific O‐Selective Hydropyridonation of Terminal Alkynes
The dinuclear complex [Rh(μ‐Cl)(η2‐coe)(IPr)]2 is an efficient catalyst for the O‐selective Markovnikov‐type addition of 2‐pyridones to terminal alkynes. DFT calculations support a hydride‐free pathway entailing intramolecular oxidative protonation of a π‐alkyne by a κ1N‐hydroxypyridine ligand. Subs...
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| Veröffentlicht in: | Angewandte Chemie 2022-05, Vol.134 (20), p.n/a |
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| container_title | Angewandte Chemie |
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| creator | Galiana‐Cameo, María Romeo, Raúl Urriolabeitia, Asier Passarelli, Vincenzo Pérez‐Torrente, Jesús J. Polo, Victor Castarlenas, Ricardo |
| description | The dinuclear complex [Rh(μ‐Cl)(η2‐coe)(IPr)]2 is an efficient catalyst for the O‐selective Markovnikov‐type addition of 2‐pyridones to terminal alkynes. DFT calculations support a hydride‐free pathway entailing intramolecular oxidative protonation of a π‐alkyne by a κ1N‐hydroxypyridine ligand. Subsequent O‐nucleophilic attack on a metallacyclopropene species affords an O‐alkenyl‐2‐oxypyridine chelate rhodium intermediate as the catalyst resting state. The release of the alkenyl ether is calculated as the rate‐determining step.
A Rh‐IPr catalyst was reported for the synthesis of gem‐O‐alkenyl‐oxypyridines by selective O‐addition of 2‐pyridones to terminal alkynes. A preferable N‐coordination mode within the metallacyclopropene intermediate species causes a seesaw effect responsible for the O‐nucleophilic attack. |
| doi_str_mv | 10.1002/ange.202117006 |
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A Rh‐IPr catalyst was reported for the synthesis of gem‐O‐alkenyl‐oxypyridines by selective O‐addition of 2‐pyridones to terminal alkynes. A preferable N‐coordination mode within the metallacyclopropene intermediate species causes a seesaw effect responsible for the O‐nucleophilic attack.</description><identifier>ISSN: 0044-8249</identifier><identifier>EISSN: 1521-3757</identifier><identifier>DOI: 10.1002/ange.202117006</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Alkenylation ; Alkyne Hydrofunctionalization ; Alkynes ; Catalysts ; Chemistry ; C−O Coupling ; Mathematical analysis ; N-Heterocyclic Carbene ; Protonation ; Pyridone ; Rhodium</subject><ispartof>Angewandte Chemie, 2022-05, Vol.134 (20), p.n/a</ispartof><rights>2022 The Authors. Angewandte Chemie 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><cites>FETCH-LOGICAL-c1576-9ad11e5e66065dfb49bb6a53e8fb0d719eddbf48134c5b26c608e245fb789bd13</cites><orcidid>0000-0001-5823-7965 ; 0000-0002-3327-0918 ; 0000-0002-2043-4864 ; 0000-0002-1735-6439 ; 0000-0003-4460-8678</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%2Fange.202117006$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fange.202117006$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids></links><search><creatorcontrib>Galiana‐Cameo, María</creatorcontrib><creatorcontrib>Romeo, Raúl</creatorcontrib><creatorcontrib>Urriolabeitia, Asier</creatorcontrib><creatorcontrib>Passarelli, Vincenzo</creatorcontrib><creatorcontrib>Pérez‐Torrente, Jesús J.</creatorcontrib><creatorcontrib>Polo, Victor</creatorcontrib><creatorcontrib>Castarlenas, Ricardo</creatorcontrib><title>Rhodium‐NHC‐Catalyzed gem‐Specific O‐Selective Hydropyridonation of Terminal Alkynes</title><title>Angewandte Chemie</title><description>The dinuclear complex [Rh(μ‐Cl)(η2‐coe)(IPr)]2 is an efficient catalyst for the O‐selective Markovnikov‐type addition of 2‐pyridones to terminal alkynes. DFT calculations support a hydride‐free pathway entailing intramolecular oxidative protonation of a π‐alkyne by a κ1N‐hydroxypyridine ligand. Subsequent O‐nucleophilic attack on a metallacyclopropene species affords an O‐alkenyl‐2‐oxypyridine chelate rhodium intermediate as the catalyst resting state. The release of the alkenyl ether is calculated as the rate‐determining step.
A Rh‐IPr catalyst was reported for the synthesis of gem‐O‐alkenyl‐oxypyridines by selective O‐addition of 2‐pyridones to terminal alkynes. 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DFT calculations support a hydride‐free pathway entailing intramolecular oxidative protonation of a π‐alkyne by a κ1N‐hydroxypyridine ligand. Subsequent O‐nucleophilic attack on a metallacyclopropene species affords an O‐alkenyl‐2‐oxypyridine chelate rhodium intermediate as the catalyst resting state. The release of the alkenyl ether is calculated as the rate‐determining step.
A Rh‐IPr catalyst was reported for the synthesis of gem‐O‐alkenyl‐oxypyridines by selective O‐addition of 2‐pyridones to terminal alkynes. A preferable N‐coordination mode within the metallacyclopropene intermediate species causes a seesaw effect responsible for the O‐nucleophilic attack.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ange.202117006</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0001-5823-7965</orcidid><orcidid>https://orcid.org/0000-0002-3327-0918</orcidid><orcidid>https://orcid.org/0000-0002-2043-4864</orcidid><orcidid>https://orcid.org/0000-0002-1735-6439</orcidid><orcidid>https://orcid.org/0000-0003-4460-8678</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Alkenylation Alkyne Hydrofunctionalization Alkynes Catalysts Chemistry C−O Coupling Mathematical analysis N-Heterocyclic Carbene Protonation Pyridone Rhodium |
| title | Rhodium‐NHC‐Catalyzed gem‐Specific O‐Selective Hydropyridonation of Terminal Alkynes |
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