C−C Bond Formation of Benzyl Alcohols and Alkynes Using a Catalytic Amount of KOtBu: Unusual Regioselectivity through a Radical Mechanism

Amit Kumar; Trevor Janes; Subrata Chakraborty; Prosenjit Daw; Niklas von Wolff; Raanan Carmieli; Yael Diskin-Posner; David Milstein

doi:10.1002/anie.201812687

C−C Bond Formation of Benzyl Alcohols and Alkynes Using a Catalytic Amount of KO^tBu: Unusual Regioselectivity through a Radical Mechanism

Amit Kumar, Trevor Janes, Subrata Chakraborty, Prosenjit Daw, Niklas von Wolff, Raanan Carmieli, Yael Diskin-Posner, David Milstein^*

^*Corresponding author for this work

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

23 Citations (Scopus)

78 Downloads (Pure)

Abstract

We report a C−C bond-forming reaction between benzyl alcohols and alkynes in the presence of a catalytic amount of KO ^t Bu to form α-alkylated ketones in which the C=O group is located on the side derived from the alcohol. The reaction proceeds under thermal conditions (125 °C) and produces no waste, making the reaction highly atom efficient, environmentally benign, and sustainable. Based on our mechanistic investigations, we propose that the reaction proceeds through radical pathways.

Original language	English
Pages (from-to)	3373-3377
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	11
DOIs	https://doi.org/10.1002/anie.201812687
Publication status	Published - 11 Mar 2019

Funding

D.M. holds the Israel Matz Professorial Chair of Organic Chemistry. A.K. and P.D. are thankful to the Israel Planning and Budgeting Commission (PBC) for a fellowship. T.J. thanks the Azrieli Foundation for a postdoctoral fellowship. N.v.W. is supported by the Foreign Postdoctoral Fellowship Program of the Israel Academy of Sciences and Humanities.

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry

Access to Document

10.1002/anie.201812687

dm_-angewandte_C-CBond_AM2019Accepted author manuscript, 1.23 MBLicence: CC BY-NC-ND

Cite this

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abstract = "We report a C−C bond-forming reaction between benzyl alcohols and alkynes in the presence of a catalytic amount of KO t Bu to form α-alkylated ketones in which the C=O group is located on the side derived from the alcohol. The reaction proceeds under thermal conditions (125 °C) and produces no waste, making the reaction highly atom efficient, environmentally benign, and sustainable. Based on our mechanistic investigations, we propose that the reaction proceeds through radical pathways. ",

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AU - Janes, Trevor

AU - Chakraborty, Subrata

AU - Daw, Prosenjit

AU - von Wolff, Niklas

AU - Carmieli, Raanan

AU - Diskin-Posner, Yael

AU - Milstein, David

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AB - We report a C−C bond-forming reaction between benzyl alcohols and alkynes in the presence of a catalytic amount of KO t Bu to form α-alkylated ketones in which the C=O group is located on the side derived from the alcohol. The reaction proceeds under thermal conditions (125 °C) and produces no waste, making the reaction highly atom efficient, environmentally benign, and sustainable. Based on our mechanistic investigations, we propose that the reaction proceeds through radical pathways.

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