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Article: A DFT study on the mechanism of Rh2 II, II-catalyzed intramolecular amidation of carbamates

TitleA DFT study on the mechanism of Rh2 II, II-catalyzed intramolecular amidation of carbamates
Authors
KeywordsAmidation
Density functional calculations
Nitrene insertion
Reaction mechanisms
Rhodium
Issue Date2007
PublisherWiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2451
Citation
Chemistry - An Asian Journal, 2007, v. 2 n. 9, p. 1101-1108 How to Cite?
AbstractThe potential-energy surfaces of the reactions of dirhodium tetracarboxylate (Rh2 II,II) catalyzed nitrene (NR) insertion into C-H bonds were examined by a DFT computational study. A pure Becke exchange functional (B88) rather than a hybrid exchange functional (B3, BHandH) was found to be appropriate for the calculation of the energy difference between the singlet and triplet Rh2 II,II-NH nitrene species. Rh2 II,II-NR1 (R1 = (S)-2-methyl-1-butylformyl) is thermodynamically more favorable with a free energy lower than that of Rh2 II, II-N-(PhI)R1. The singlet and triplet states of Rh 2 II,II-NR1 have similar stability. Singlet Rh2 II,II-NR1 undergoes a concerted NR insertion into the C-H bond with simultaneous formation of the N-H and N-C bonds during C-H bond cleavage; triplet Rh2 II,II-NR1 undergoes H atom abstraction to produce a diradical, followed by subsequent bond formation by diradical recombination. The singlet pathway is favored over the triplet in the context of the free energy of activation and leads to the retention of the chirality of the C atom in the NR insertion product. The reactivities of the C-H bonds toward the nitrene-insertion reaction follow the order tertiary > secondary > primary. Relative reaction rates were calculated for the six reaction pathways examined in this work. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Persistent Identifierhttp://hdl.handle.net/10722/70112
ISSN
2015 Impact Factor: 4.592
2015 SCImago Journal Rankings: 1.833
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLin, Xen_HK
dc.contributor.authorZhao, Cen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorKe, Zen_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2010-09-06T06:19:50Z-
dc.date.available2010-09-06T06:19:50Z-
dc.date.issued2007en_HK
dc.identifier.citationChemistry - An Asian Journal, 2007, v. 2 n. 9, p. 1101-1108en_HK
dc.identifier.issn1861-4728en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70112-
dc.description.abstractThe potential-energy surfaces of the reactions of dirhodium tetracarboxylate (Rh2 II,II) catalyzed nitrene (NR) insertion into C-H bonds were examined by a DFT computational study. A pure Becke exchange functional (B88) rather than a hybrid exchange functional (B3, BHandH) was found to be appropriate for the calculation of the energy difference between the singlet and triplet Rh2 II,II-NH nitrene species. Rh2 II,II-NR1 (R1 = (S)-2-methyl-1-butylformyl) is thermodynamically more favorable with a free energy lower than that of Rh2 II, II-N-(PhI)R1. The singlet and triplet states of Rh 2 II,II-NR1 have similar stability. Singlet Rh2 II,II-NR1 undergoes a concerted NR insertion into the C-H bond with simultaneous formation of the N-H and N-C bonds during C-H bond cleavage; triplet Rh2 II,II-NR1 undergoes H atom abstraction to produce a diradical, followed by subsequent bond formation by diradical recombination. The singlet pathway is favored over the triplet in the context of the free energy of activation and leads to the retention of the chirality of the C atom in the NR insertion product. The reactivities of the C-H bonds toward the nitrene-insertion reaction follow the order tertiary > secondary > primary. Relative reaction rates were calculated for the six reaction pathways examined in this work. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.en_HK
dc.languageengen_HK
dc.publisherWiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2451en_HK
dc.relation.ispartofChemistry - An Asian Journalen_HK
dc.subjectAmidationen_HK
dc.subjectDensity functional calculationsen_HK
dc.subjectNitrene insertionen_HK
dc.subjectReaction mechanismsen_HK
dc.subjectRhodiumen_HK
dc.subject.meshAmides - chemistry-
dc.subject.meshCarbamates - chemistry-
dc.subject.meshCatalysis-
dc.subject.meshOrganometallic Compounds - chemistry-
dc.subject.meshThermodynamics-
dc.titleA DFT study on the mechanism of Rh2 II, II-catalyzed intramolecular amidation of carbamatesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1861-4728&volume=2&issue=9&spage=1101&epage=1108&date=2007&atitle=A+DFT+study+on+the+mechanism+of+Rh2(II,II)-catalyzed+intramolecular+amidation+of+carbamatesen_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/asia.200700068en_HK
dc.identifier.pmid17712831-
dc.identifier.scopuseid_2-s2.0-34548585780en_HK
dc.identifier.hkuros137278en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-34548585780&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume2en_HK
dc.identifier.issue9en_HK
dc.identifier.spage1101en_HK
dc.identifier.epage1108en_HK
dc.identifier.isiWOS:000249294600004-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridLin, X=35205535200en_HK
dc.identifier.scopusauthoridZhao, C=7403563836en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridKe, Z=14048262500en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK

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