Activation of Carbon-Carbon Bonds by Soluble Transition Metals

• Project/Area Number: 08455426
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: KYOTO UNIVERSITY
• Principal Investigator: MURAKAMI Masanori Kyoto University, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (20174279)
• Project Period (FY): 1996 – 1998
• Project Status: Completed (Fiscal Year 1998)
• Budget Amount: ¥6,300,000 (Direct Cost: ¥6,300,000); Fiscal Year 1998: ¥1,500,000 (Direct Cost: ¥1,500,000); Fiscal Year 1997: ¥1,500,000 (Direct Cost: ¥1,500,000); Fiscal Year 1996: ¥3,300,000 (Direct Cost: ¥3,300,000)
• Keywords: Activation of C-C Bonds / Hydrogenolysis / Rhodium / Cyclobutanone / Decarbonylation / Catalytic Reactions / 酸化的付加 / β-酸素脱離

Research Abstract

Rhodium(I)-catalyzed synthetic transformations involving selective breaking of the C-C bond alpha to the carbonyl group of cyclobutanones was studied. Decarbonylation took place on treatment of a cyclobutanone with an equimolar amount of (Ph_3P)_3RhCl at reflux in toluene to afford the corresponding cyclopropane. The formation of the cyclopropane suggests that Rh(I) undergoes an insertion into the bond between the carbonyl carbon and the alpha-carbon in the initial step. Catalytic decarbonylation of cyclobutanone was also achieved. The mode and rate of the reaction depended greatly on the ligands of the rhodium(I) complex. When a cyclobutanone bearing a hydrogen atom at the 3-position was used, appropriate choice of the catalyst system led to the selective formation of either a cyclopropane or an alkene.
Hydrogenolysis of cyclohexanone was next attempted. Various reaction conditions including ligands, hydrogen pressure, and solvent were examined, hydrogenolysis of cyclohexanone failed to proceed efficiently. Other metals like ruthenium and iridium were found to be ineffective. We will continue to investigate selective breaking of C-C bonds of ordinary ketones by a soluble transition metal complex.

Research Products

• [Publications] Masahiro Murakami: "Breaking of the C-C Bond of Cycloburanones by Rhodium (I) and Its extension to Catalytic Synthetic Reactions" J.Am.Chem.Soc.118・35. 8285-8290 (1996)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Masahiro Murakami: "Breaking of the C-C Bond of Cyclobutanones by Rhodium (I) and Its Extension to Catalytic Synthetic Reactions" J.Am.Chem.Soc.118-35. 8285-8290 (1996)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Masahiro Murakami: "Breaking of the C-C Bond of Cyclobutanones by Rhodium(I) and Its Extension to Catalytic Synthetic Reactions" J.Am.Chem.Soc.118・35. 8285-8290 (1996)
• [Publications] Masahiro Murakami: "Rhodium(I)-Catalyzed Successive Double Cleavege of Carbon-Carbon Bonds of Strained Spiro Cyclobutanones" J.Am.Chem.Soc.119・39. 9307-9308 (1997)
• [Publications] Masahiro Murakami: "New Domino Sequences Involving Successive Cleavage of Carbon-Carbon and Carbon-Oxygen Bonds: Discrete Product Selection Dictated by Catalyst Ligands" J.Am.Chem.Soc.120・38. 9949-9950 (1998)
• [Publications] M.Murakami, K.Takahashi, H.Amii, Y.Ito: "Rhodium (I)-Catalyzed Successive Double Cleavage of Carbon-Carbon Bonds of Strained Spiro Cyclobutanones" Journal of the American Chemical Society. 119. 9307-9308 (1997)
• [Publications] Masahiro Murakami: "Breaking of the C-C Bond of Cyclobutanones by Rhodium (I) and Its extension to Catalytic Synthetic Reactions21GC01:J.Am.Chem.Soc." 118・35. 8285-8290 (1996)