Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions

Nguyen, Hoang Ngan; Tashima, Naoto; Ikariya, Takao; Kuwata, Shigeki

doi:10.3390/inorganics5040080

Open AccessArticle

Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions

by

Hoang Ngan Nguyen

¹,

Naoto Tashima

¹,

Takao Ikariya

¹ and

Shigeki Kuwata

^1,2,*

¹

Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 E4-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan

²

Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan

^*

Author to whom correspondence should be addressed.

Inorganics 2017, 5(4), 80; https://doi.org/10.3390/inorganics5040080

Submission received: 28 October 2017 / Revised: 14 November 2017 / Accepted: 14 November 2017 / Published: 16 November 2017

(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)

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Abstract

Propargyl alcohol is a useful synthon in synthetic organic chemistry. We found that the ruthenium(II) complex [Cp*RuCl(diene)] (Cp* = η⁵-C₅Me₅; diene = isoprene or 1,5-cyclooctadiene (cod)) catalyzes dimerization of 1,1-diphenylprop-2-yn-1-ol (1,1-diphenylpropargyl alcohol, 1a) at room temperature to afford an alkylidenebenzocyclobutenyl alcohol 2a quantitatively. Meanwhile, a stoichiometric reaction of the related hydrido complex [Cp*RuH(cod)] with 1a at 50 °C led to isolation of a ruthenocene derivative 4 bearing a cyclopentadienyl ring generated by dehydrogenative trimerization of 1a. Detailed structures of 2a and 4 were determined by X-ray crystallography. The reaction mechanisms for the formation of 2a and 4 were proposed.

Keywords: ruthenium; alkyne; propargyl alcohol; C–H cleavage; benzocyclobutene

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MDPI and ACS Style

Nguyen, H.N.; Tashima, N.; Ikariya, T.; Kuwata, S. Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions. Inorganics 2017, 5, 80. https://doi.org/10.3390/inorganics5040080

AMA Style

Nguyen HN, Tashima N, Ikariya T, Kuwata S. Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions. Inorganics. 2017; 5(4):80. https://doi.org/10.3390/inorganics5040080

Chicago/Turabian Style

Nguyen, Hoang Ngan, Naoto Tashima, Takao Ikariya, and Shigeki Kuwata. 2017. "Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions" Inorganics 5, no. 4: 80. https://doi.org/10.3390/inorganics5040080

APA Style

Nguyen, H. N., Tashima, N., Ikariya, T., & Kuwata, S. (2017). Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions. Inorganics, 5(4), 80. https://doi.org/10.3390/inorganics5040080

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Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions

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