Rhodium(I)-Catalyzed CO-Gas-Free Arylative Dual-Carbonylation of Alkynes with Arylboronic Acids via the Formyl C–H Activation of Formaldehyde

Tsumoru Morimoto; Chuang Wang; Hiroki Tanimoto; Levent Artok; Kiyomi Kakiuchi

doi:10.1055/a-1468-8377

Synthesis, Table of Contents

Synthesis 2021; 53(18): 3372-3382
DOI: 10.1055/a-1468-8377

special topic

Bond Activation – in Honor of Prof. Shinji Murai

Rhodium(I)-Catalyzed CO-Gas-Free Arylative Dual-Carbonylation of Alkynes with Arylboronic Acids via the Formyl C–H Activation of Formaldehyde

Tsumoru Morimoto ∗

^aDivision of Materials Science, Graduate School of Science and Technology, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan

,

Chuang Wang

^aDivision of Materials Science, Graduate School of Science and Technology, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan

,

Hiroki Tanimoto

^bAcademic Assembly, Faculty of Pharmaceutical Sciences, University of Toyama, 2630 Sugitani, Toyama 930-0194, Japan

,

Levent Artok

^cDepartment of Chemistry, Faculty of Science, Izmir Institute of Technology, Urla 35430, Izmir, Turkey

,

Kiyomi Kakiuchi

^aDivision of Materials Science, Graduate School of Science and Technology, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan

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Abstract

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Abstract

The rhodium(I)-catalyzed reaction of alkynes with arylboronic acids in the presence of formaldehyde results in a CO-gas-free arylative dual-carbonylation to produce γ-butenolide derivatives. The simultaneous loading of phosphine-ligated and phosphine-free rhodium(I) complexes is required for efficient catalysis. The former complex catalyzes the abstraction of a carbonyl moiety from formaldehyde through the activation of its formyl C–H bond (decarbonylation) and the latter catalyzes the subsequent dual-incorporation of the resulting carbonyl unit (carbonylation). The use of larger amounts of the phosphine-ligated rhodium(I) complex generates more carbonyl units, leading to the formation γ-butenolides via the dual-incorporation of the carbonyl unit.

Key words

C–H activation - decarbonylation - rhodium - formaldehyde - γ-butenolides - alkynes - arylboronic acids

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References

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