Pd-Catalyzed Copolymerization of Methyl Acrylate with Carbon Monoxide: Structures, Properties and Mechanistic Aspects toward Ligand Design

Akifumi Nakamura; Kagehiro Munakata; Shingo Ito; Takuya Kochi; Lung Wa Chung; Keiji Morokuma; Kyoko Nozaki

doi:10.1021/ja2003268

Pd-Catalyzed Copolymerization of Methyl Acrylate with Carbon Monoxide: Structures, Properties and Mechanistic Aspects toward Ligand Design

Journal of the American Chemical Society ◽

10.1021/ja2003268 ◽

2011 ◽

Vol 133 (17) ◽

pp. 6761-6779 ◽

Cited By ~ 53

Author(s):

Akifumi Nakamura ◽

Kagehiro Munakata ◽

Shingo Ito ◽

Takuya Kochi ◽

Lung Wa Chung ◽

...

Keyword(s):

Carbon Monoxide ◽

Methyl Acrylate ◽

Ligand Design

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Catalytic synthesis of methyl acrylate from acetylene, carbon monoxide and methanol under pressure

Journal of Biochemical Toxicology ◽

10.1002/jbt.2570131104 ◽

1963 ◽

Vol 13 (11) ◽

pp. 498-505

Author(s):

S. K. Bhattacharyya ◽

A. K. Sen

Keyword(s):

Carbon Monoxide ◽

Methyl Acrylate ◽

Catalytic Synthesis ◽

Acetylene Carbon

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Ruthenium- and Rhodium-Catalyzed Ring-Opening Coupling Reactions of Cyclopropenones with Alkenes or Alkynes

Synlett ◽

10.1055/s-0037-1609339 ◽

2018 ◽

Vol 29 (06) ◽

pp. 717-722 ◽

Cited By ~ 8

Author(s):

Teruyuki Kondo ◽

Ryosuke Taniguchi ◽

Yu Kimura

Keyword(s):

Carbon Monoxide ◽

Catalytic Activity ◽

Methyl Acrylate ◽

Ring Opening ◽

Argon Atmosphere ◽

High Catalytic Activity ◽

Rhodium Complexes ◽

Coupling Reactions ◽

Internal Alkynes ◽

High Yields

Ru3(CO)12-catalyzed divergent ring-opening coupling reactions of a cyclopropenone with methyl acrylate (an electron-deficient alkene) are developed. Under an argon atmosphere, a decarbonylative linear codimer is obtained, while cyclopentenones are obtained under carbon monoxide (20 atm) without decarbonylation. While ruthenium complexes show no catalytic activity for the ring-opening cocyclization of cyclopropenones with ethylene (20 atm) or bicyclo[2.2.1]hept-2-ene (2-norbornene), rhodium complexes, especially [RhCl(η4-1,5-cod)]2, show high catalytic activity for the desired cocyclization reactions to give the corresponding cyclopentenones in high yields and selectivities. In addition, [RhCl(η4-1,5-cod)]2 realizes the catalytic ring-opening cocyclization of cyclopropenones with internal alkynes to give the corresponding cyclopentadienones. In all these reactions, ruthena- or rhodacyclobutenones are considered to be key intermediates, generated by strain-driven oxidative addition of a cyclopropenone C–C bond to an active ruthenium or rhodium species.

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