Development of Catalytic Reactions involving Late Transition-metal Vinylidene Species Bearing Hard Ligands

2015 Fiscal Year Final Research Report

• Project/Area Number: 24350050
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Keio University
• Principal Investigator: Kakiuchi Fumitoshi 慶應義塾大学, 理工学部, 教授 (70252591)
• Co-Investigator(Kenkyū-buntansha): Kochi Takuya 慶應義塾大学, 理工学部, 専任講師 (70396779)
• Project Period (FY): 2012-04-01 – 2016-03-31
• Keywords: キノリノラト錯体 / ロジウム / ビニリデン錯体 / 末端アルキン / シクロブテン類 / シクロペンテン類 / アルキン二量化 / 求核攻撃

Outline of Final Research Achievements

Developments of new catalytic reactions using rhodium-quinolinolato complexes as catalysts have been investigated. We have developed the [Rh(Q)(cod)]-catalyzed 2:1 coupling reaction of terminal alkyne and active methylene compounds leading to cyclopentene derivatives. We found that the coupling of aliphatic alkynes with alkyl acrylates gave cyclobutene derivatives in regioselective manner in high yields. In addition, we synthesized PNO tridentate ligands bearing diphenylphosphinomethylene group at 2-position of the quinolinolate moiety and prepared new types of rhodium complexes having this PNO tridentate ligand.

Free Research Field

有機合成化学