DC Field | Value | Language |
---|---|---|
dc.contributor.author | Choi, Hyoju | ko |
dc.contributor.author | Wang, Ruibin | ko |
dc.contributor.author | Kim, Suyeon | ko |
dc.contributor.author | Kim, Dongwook | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.contributor.author | Park, Sehoon | ko |
dc.date.accessioned | 2023-05-25T01:00:22Z | - |
dc.date.available | 2023-05-25T01:00:22Z | - |
dc.date.created | 2023-05-12 | - |
dc.date.created | 2023-05-12 | - |
dc.date.created | 2023-05-12 | - |
dc.date.issued | 2023-03 | - |
dc.identifier.citation | CATALYSIS SCIENCE & TECHNOLOGY, v.13, no.9, pp.2735 - 2747 | - |
dc.identifier.issn | 2044-4753 | - |
dc.identifier.uri | http://hdl.handle.net/10203/306908 | - |
dc.description.abstract | Rhodium-catalyzed hydroboration of unsaturated organic molecules is a well-established reaction and conventionally operates via a Rh(I/III) cycle involving an inner-sphere hydride transfer. Suginome previously applied a Rh-PCy3 catalyst for the hydroboration of pyridines to selectively produce the corresponding 1,2-dihydropyridines. We now found that PPh3 in combination with [Rh(cod)Cl](2) as a precatalyst (P/Rh = 1 or 2, cod = 1,5-cyclooctadiene) brought about a mixture of N-Bpin-1,2,3,4-tetrahydropyridines bearing an sp(3) C-B bond in the C4-(G) or C3-(R) position in 60-90% combined yields, representing the first example of double hydroboration of pyridine. A series of catalytic and stoichiometric reactions under variable conditions revealed that: (1) G and R are generated from the 1,2-dihydropyridine intermediate, not the 1,4-dihydropyridine; (2) the ratio of G and R varies from similar to 1 : 2 to 5 : 1 depending on phosphine ligands; and (3) the observable Rh species in solution include Rh(PPh3)Cl(H)(Bpin)(Py)(n) (n = 1 and/or 2; Py = pyridine) as the resting state, in addition to Rh(trans-PPh3)(2)Cl(H)(Bpin) and Rh(PPh3)(cod)Cl. Density functional theory (DFT) calculations are conducted to propose plausible reaction mechanisms and reveal the origin of the chemo- and the regioselectivity in the consecutive Rh-catalyzed hydroborations to deliver the final products G and R in one-pot. | - |
dc.language | English | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | Rhodium-catalyzed double hydroboration of pyridine: the origin of the chemo- and regioselectivities | - |
dc.type | Article | - |
dc.identifier.wosid | 000968496700001 | - |
dc.identifier.scopusid | 2-s2.0-85152116695 | - |
dc.type.rims | ART | - |
dc.citation.volume | 13 | - |
dc.citation.issue | 9 | - |
dc.citation.beginningpage | 2735 | - |
dc.citation.endingpage | 2747 | - |
dc.citation.publicationname | CATALYSIS SCIENCE & TECHNOLOGY | - |
dc.identifier.doi | 10.1039/d3cy00347g | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Wang, Ruibin | - |
dc.contributor.nonIdAuthor | Park, Sehoon | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | TRANSITION-METAL-COMPLEXES | - |
dc.subject.keywordPlus | SOLVATION FREE-ENERGIES | - |
dc.subject.keywordPlus | N-HETEROARENES | - |
dc.subject.keywordPlus | ASYMMETRIC HYDROGENATION | - |
dc.subject.keywordPlus | HETEROAROMATIC-COMPOUNDS | - |
dc.subject.keywordPlus | SILYLATIVE REDUCTION | - |
dc.subject.keywordPlus | CHEMISTRY | - |
dc.subject.keywordPlus | HYDRIDE | - |
dc.subject.keywordPlus | DEAROMATIZATION | - |
dc.subject.keywordPlus | BORON | - |
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