TY - JOUR
T1 - Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides
AU - Hou, Duenren
AU - Kuan, Tingchun
AU - Li, YuKai
AU - Lee, Richmond
AU - Huang, Kuo-Wei
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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.
PY - 2010/11
Y1 - 2010/11
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/561561
UR - https://linkinghub.elsevier.com/retrieve/pii/S004040201001464X
UR - http://www.scopus.com/inward/record.url?scp=78049462274&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2010.09.099
DO - 10.1016/j.tet.2010.09.099
M3 - Article
SN - 0040-4020
VL - 66
SP - 9415
EP - 9420
JO - Tetrahedron
JF - Tetrahedron
IS - 48
ER -