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

Duenren Hou; Tingchun Kuan; YuKai Li; Richmond Lee; Kuo-Wei Huang

doi:10.1016/j.tet.2010.09.099

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

Duenren Hou, Tingchun Kuan, YuKai Li, Richmond Lee, Kuo-Wei Huang

Research output: Contribution to journal › Article › peer-review

35 Scopus citations

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.

Original language	English (US)
Pages (from-to)	9415-9420
Number of pages	6
Journal	Tetrahedron
Volume	66
Issue number	48
DOIs	https://doi.org/10.1016/j.tet.2010.09.099
State	Published - Nov 2010

Bibliographical note

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.

ASJC Scopus subject areas

Biochemistry
Organic Chemistry
Drug Discovery

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title = "Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides",

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. {\textcopyright} 2010 Elsevier Ltd. All rights reserved.",

author = "Duenren Hou and Tingchun Kuan and YuKai Li and Richmond Lee and Kuo-Wei Huang",

note = "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.",

year = "2010",

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doi = "10.1016/j.tet.2010.09.099",

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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.

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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.

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

Abstract

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