Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides

Handle URI:
http://hdl.handle.net/10754/561561
Title:
Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides
Authors:
Hou, Duenren; Kuan, Tingchun; Li, YuKai; Lee, Richmond; Huang, Kuo-Wei ( 0000-0003-1900-2658 )
Abstract:
A combined experimental and theoretical study of ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) reactions is presented and various electronic analyses were conducted to provide a basis in understanding the observed regioselectivity of the 1,2,3-triazole products. Computational studies using density functional theory (DFT) and atoms in molecules quantum theory (AIM) further yield fresh details on the electronic factors that determine the regioselectivity in the RuAAC. It is found that the formation of 1,2,3-triazole products is irreversible and from the Hammett study, the pathway involving a vinyl cationic intermediate is ruled out. The electronic effect favors the formation of 5-electron-donating-group substituted-1,2,3-trizoles. © 2010 Elsevier Ltd. All rights reserved.
KAUST Department:
Biological and Environmental Sciences and Engineering (BESE) Division; KAUST Catalysis Center (KCC); Chemical Science Program; Physical Sciences and Engineering (PSE) Division; HCL
Publisher:
Elsevier BV
Journal:
Tetrahedron
Issue Date:
Nov-2010
DOI:
10.1016/j.tet.2010.09.099
Type:
Article
ISSN:
00404020
Sponsors:
We acknowledge the financial support from NSC (95-2113-M-008-007-MY3) to D.-R.H., from National University of Singapore (R-143-000-346-133 and R-143-000-376-112) and KAUST (400000 0076) to K.-W.H. R.L. is grateful for a Provost fellowship from KAUST. We are indebted to Dr. Dodi Heryadi of KAUST Super-computing Laboratory for advice on computational chemistry and to Prof. Jorg Eppinger for useful discussions.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorHou, Duenrenen
dc.contributor.authorKuan, Tingchunen
dc.contributor.authorLi, YuKaien
dc.contributor.authorLee, Richmonden
dc.contributor.authorHuang, Kuo-Weien
dc.date.accessioned2015-08-02T09:14:14Zen
dc.date.available2015-08-02T09:14:14Zen
dc.date.issued2010-11en
dc.identifier.issn00404020en
dc.identifier.doi10.1016/j.tet.2010.09.099en
dc.identifier.urihttp://hdl.handle.net/10754/561561en
dc.description.abstractA combined experimental and theoretical study of ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) reactions is presented and various electronic analyses were conducted to provide a basis in understanding the observed regioselectivity of the 1,2,3-triazole products. Computational studies using density functional theory (DFT) and atoms in molecules quantum theory (AIM) further yield fresh details on the electronic factors that determine the regioselectivity in the RuAAC. It is found that the formation of 1,2,3-triazole products is irreversible and from the Hammett study, the pathway involving a vinyl cationic intermediate is ruled out. The electronic effect favors the formation of 5-electron-donating-group substituted-1,2,3-trizoles. © 2010 Elsevier Ltd. All rights reserved.en
dc.description.sponsorshipWe acknowledge the financial support from NSC (95-2113-M-008-007-MY3) to D.-R.H., from National University of Singapore (R-143-000-346-133 and R-143-000-376-112) and KAUST (400000 0076) to K.-W.H. R.L. is grateful for a Provost fellowship from KAUST. We are indebted to Dr. Dodi Heryadi of KAUST Super-computing Laboratory for advice on computational chemistry and to Prof. Jorg Eppinger for useful discussions.en
dc.publisherElsevier BVen
dc.titleElectronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azidesen
dc.typeArticleen
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentHCLen
dc.identifier.journalTetrahedronen
dc.contributor.institutionDepartment of Chemistry, National Central University, 300 Jhong-Da Rd., Jhong-Li, Taoyuan 32001, Taiwanen
dc.contributor.institutionDepartment of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singaporeen
kaust.authorLee, Richmonden
kaust.authorHuang, Kuo-Weien
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