The origin of the ligand-controlled regioselectivity in Rh-catalyzed [(2 + 2) + 2] carbocyclizations: steric vs. stereoelectronic effects
DC Field | Value | Language |
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dc.contributor.author | Crandell, D.W. | - |
dc.contributor.author | Mazumder, S. | - |
dc.contributor.author | Evans, P.A. | - |
dc.contributor.author | Mu-Hyun Baik | - |
dc.date.available | 2016-01-25T00:11:26Z | - |
dc.date.created | 2015-12-21 | - |
dc.date.issued | 2015-12 | - |
dc.identifier.issn | 2041-6520 | - |
dc.identifier.uri | https://pr.ibs.re.kr/handle/8788114/2232 | - |
dc.description.abstract | Density functional theory calculations demonstrate that the reversal of regiochemical outcome of the addition for substituted methyl propiolates in the rhodium-catalyzed [(2 + 2) + 2] carbocyclization with PPh3 and (S)-xyl-binap as ligands is both electronically and sterically controlled. For example, the ester functionality polarizes the alkyne π∗ orbital to favor overlap of the methyl-substituted terminus of the alkyne with the pπ-orbital of the alkenyl fragment of the rhodacycle during alkyne insertion with PPh3 as the ligand. In contrast, the sterically demanding xyl-binap ligand cannot accommodate the analogous alkyne orientation, thereby forcing insertion to occur at the sterically preferred ester terminus, overriding the electronically preferred orientation for alkyne insertion. © The Royal Society of Chemistry | - |
dc.description.uri | 1 | - |
dc.language | 영어 | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | The origin of the ligand-controlled regioselectivity in Rh-catalyzed [(2 + 2) + 2] carbocyclizations: steric vs. stereoelectronic effects | - |
dc.type | Article | - |
dc.type.rims | ART | - |
dc.identifier.wosid | 000365225300025 | - |
dc.identifier.scopusid | 2-s2.0-84946566806 | - |
dc.identifier.rimsid | 21788 | - |
dc.date.tcdate | 2018-10-01 | - |
dc.contributor.affiliatedAuthor | Mu-Hyun Baik | - |
dc.identifier.doi | 10.1039/c5sc02307f | - |
dc.identifier.bibliographicCitation | CHEMICAL SCIENCE, v.6, no.12, pp.6896 - 6900 | - |
dc.citation.title | CHEMICAL SCIENCE | - |
dc.citation.volume | 6 | - |
dc.citation.number | 12 | - |
dc.citation.startPage | 6896 | - |
dc.citation.endPage | 6900 | - |
dc.date.scptcdate | 2018-10-01 | - |
dc.description.wostc | 2 | - |
dc.description.scptc | 3 | - |
dc.description.journalClass | 1 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |