Rationally Designing Regiodivergent Dipolar Cycloadditions: Frontier Orbitals Show How To Switch between [5+3] and [4+2] Cycloadditions
DC Field | Value | Language |
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dc.contributor.author | Seung-yeol Baek | - |
dc.contributor.author | Ju Young Lee | - |
dc.contributor.author | Donguk Ko | - |
dc.contributor.author | Mu-Hyun Baik | - |
dc.contributor.author | Eun Jeong Yoo | - |
dc.date.available | 2019-07-19T05:41:02Z | - |
dc.date.created | 2019-06-19 | - |
dc.date.issued | 2018-07 | - |
dc.identifier.issn | 2155-5435 | - |
dc.identifier.uri | https://pr.ibs.re.kr/handle/8788114/5923 | - |
dc.description.abstract | A pyridinium zwitterion substrate is employed with two different types of transition metal catalysts to develop a regiodivergent cycloaddition. The pyridinium zwitterion is a highly reactive dipolar substrate that can undergo a dipolar cycloaddition with various reactants. It has multiple reaction sites, and the chemoselectivity is determined by the electronic demand of the catalyst substrate complex. The reaction with nucleophilic Pd reagents affords fused N-heterocyclic compounds via regioselective [4 + 2] cycloaddition. The origin of the site selectivity and the mechanism of this reaction are investigated in this combined experimental and computational study. We found that the pyridinium zwitterion plays a completely different role in the palladium(0)-catalyzed [4 + 2] cycloaddition reaction and in the rhodium(II)-catalyzed [5 + 3] cycloaddition, which was examined experimentally in a previous study. The frontier molecular orbitals of the pyridinium substrate and activated catalyst complex reveal that the pyridinium zwitterion can act as both a nucleophile and an electrophile depending on the reaction partner in a manner much more defined than that of conventional substrates, leading to the observed regiodivergent chemical reactivity. | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | regiodivergent cycloaddition | - |
dc.subject | pyridinium zwitterion | - |
dc.subject | chemical reactivity | - |
dc.subject | vinylcyclopropanes | - |
dc.title | Rationally Designing Regiodivergent Dipolar Cycloadditions: Frontier Orbitals Show How To Switch between [5+3] and [4+2] Cycloadditions | - |
dc.type | Article | - |
dc.type.rims | ART | - |
dc.identifier.wosid | 000438475100070 | - |
dc.identifier.scopusid | 2-s2.0-85047544524 | - |
dc.identifier.rimsid | 68720 | - |
dc.contributor.affiliatedAuthor | Seung-yeol Baek | - |
dc.contributor.affiliatedAuthor | Mu-Hyun Baik | - |
dc.identifier.doi | 10.1021/acscatal.8b00845 | - |
dc.identifier.bibliographicCitation | ACS CATALYSIS, v.8, no.7, pp.6353 - 6361 | - |
dc.relation.isPartOf | ACS CATALYSIS | - |
dc.citation.title | ACS CATALYSIS | - |
dc.citation.volume | 8 | - |
dc.citation.number | 7 | - |
dc.citation.startPage | 6353 | - |
dc.citation.endPage | 6361 | - |
dc.description.journalClass | 1 | - |
dc.description.journalClass | 1 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Physical | - |
dc.subject.keywordPlus | EFFECTIVE CORE POTENTIALS | - |
dc.subject.keywordPlus | SOLVATION FREE-ENERGIES | - |
dc.subject.keywordPlus | MOLECULAR CALCULATIONS | - |
dc.subject.keywordPlus | METAL | - |
dc.subject.keywordPlus | VINYLCYCLOPROPANES | - |
dc.subject.keywordPlus | MECHANISM | - |
dc.subject.keywordPlus | CARBOCYCLIZATION | - |
dc.subject.keywordPlus | SELECTIVITY | - |
dc.subject.keywordPlus | PYRIDINE | - |
dc.subject.keywordPlus | ALLENES | - |
dc.subject.keywordAuthor | regiodivergent cycloaddition | - |
dc.subject.keywordAuthor | pyridinium zwitterion | - |
dc.subject.keywordAuthor | chemical reactivity | - |
dc.subject.keywordAuthor | vinylcyclopropanes | - |