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

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

Weizmann Institute of Science, Israel

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

12 Citations (Scopus)

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 - Mar 11 2019

Keywords

alkynes
benzyl alcohols
potassium tert-butoxide
radicals
α-alkylated ketones

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.201812687

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Kumar, A., Janes, T., Chakraborty, S., Daw, P., von Wolff, N., Carmieli, R., Diskin-Posner, Y., & Milstein, D. (2019). C−C Bond Formation of Benzyl Alcohols and Alkynes Using a Catalytic Amount of KO ^t Bu: Unusual Regioselectivity through a Radical Mechanism. Angewandte Chemie - International Edition, 58(11), 3373-3377. https://doi.org/10.1002/anie.201812687

C−C Bond Formation of Benzyl Alcohols and Alkynes Using a Catalytic Amount of KO ^t Bu : Unusual Regioselectivity through a Radical Mechanism. / Kumar, Amit; Janes, Trevor; Chakraborty, Subrata; Daw, Prosenjit; von Wolff, Niklas; Carmieli, Raanan; Diskin-Posner, Yael; Milstein, David.

In: Angewandte Chemie - International Edition, Vol. 58, No. 11, 11.03.2019, p. 3373-3377.

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

Kumar, A, Janes, T, Chakraborty, S, Daw, P, von Wolff, N, Carmieli, R, Diskin-Posner, Y & Milstein, D 2019, 'C−C Bond Formation of Benzyl Alcohols and Alkynes Using a Catalytic Amount of KO ^t Bu: Unusual Regioselectivity through a Radical Mechanism', Angewandte Chemie - International Edition, vol. 58, no. 11, pp. 3373-3377. https://doi.org/10.1002/anie.201812687

Kumar A, Janes T, Chakraborty S, Daw P, von Wolff N, Carmieli R et al. C−C Bond Formation of Benzyl Alcohols and Alkynes Using a Catalytic Amount of KO ^t Bu: Unusual Regioselectivity through a Radical Mechanism. Angewandte Chemie - International Edition. 2019 Mar 11;58(11):3373-3377. https://doi.org/10.1002/anie.201812687

Kumar, Amit ; Janes, Trevor ; Chakraborty, Subrata ; Daw, Prosenjit ; von Wolff, Niklas ; Carmieli, Raanan ; Diskin-Posner, Yael ; Milstein, David. / C−C Bond Formation of Benzyl Alcohols and Alkynes Using a Catalytic Amount of KO ^t Bu : Unusual Regioselectivity through a Radical Mechanism. In: Angewandte Chemie - International Edition. 2019 ; Vol. 58, No. 11. pp. 3373-3377.

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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. ",

keywords = "alkynes, benzyl alcohols, potassium tert-butoxide, radicals, α-alkylated ketones",

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note = "Funding Information: D.M. holds the Israel Matz Professorial Chair of Organic Chemistry. A.K. is thankful to the Israel Planning and Budgeting Commission (PBC) for a fellowship. T.J. thanks the Azrieli Foundation for a postdoctoral fellowship. P.D. thanks the PBC and Koshland Foundation for the Senior Postdoctoral Fellowship. N.v.W. is supported by the Foreign Postdoctoral Fellowship Program of the Israel Academy of Sciences and Humanities. We are thankful to Prof. Ronny Neumann, Prof. Rafal Klajn and their research group members (Dr. Eynat Haviv from the Neumann group and Mr. Pankaj Maity and Dr. Saumen De from the Klajn group) for their help with the instrumentation facility.",

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