Studies on the Synthesis and the Application of New Functionalized Phosphines

Research Project

Project/Area Number	60550596
Research Category	Grant-in-Aid for General Scientific Research (C)
Allocation Type	Single-year Grants
Research Field	有機工業化学
Research Institution	Kyushu Institute of Technology
Principal Investigator	MINAMI Toru Kyushu Institute of Technology, 工学部, 教授 (10029134)
Co-Investigator(Kenkyū-buntansha)	YAMAGUCHI Masahiko Kyushu Institute of Technology, 工学部, 助教授 (30158117)
Project Period (FY)	1985 – 1986
Project Status	Completed (Fiscal Year 1986)
Budget Amount *help	¥2,200,000 (Direct Cost: ¥2,200,000) Fiscal Year 1986: ¥800,000 (Direct Cost: ¥800,000) Fiscal Year 1985: ¥1,400,000 (Direct Cost: ¥1,400,000)
Keywords	Chiral Diphosphine Ligand / trans-Bis-1,2-(Diphenylphosphino)cyclobutane / Rhodium (I) Complex / Asymmetric Hydrogenation / (2-Diethoxyphosphinylcyclobutyl)triphenylphosphonium Salt / Double Wittig Reaction / 1,2-Difunctionalized Cyclobutanes / 連続Diels-Alder反応
Research Abstract	In this project, the synthesis and the application of new functionalized phosphines were studied. In chapter 1, oxidative coupling of <alpha> , <omega> -phosphoryl-stabilized dicarbanions with Cu <Cl_2> led to 1,2-bis(diphenylphosphinyl)cyclobutanes. The effect of the methylene numbers of <alpha> , <omega> -diphosphine oxides on the cyclization was examined. The resolution of ( <-_+> )-trans-bis-1,2-(diphenylphosphinyl)cyclobutane (abbreviated DPCB oxide) with L-(-)-dibenzoyltartaric acid gave pure (-)-DPCB oxide, which was reduced with trichlorosilane to lead to optically active (+)-trans-bis-1,2-(diphenylphosphino)cyclobutane (abbreviated DPCB). The absolute configuration of trans-DPCB was determined by X-ray analysis of its Ni <Cl_2> complex. The asymmetric hydrogenation of dehydroamino acids catalyzed by a new type of cationic rhodium (I) complex [Rh・(+)-DPCB・(1,5-COD)] <^+BF_4^-> successfully gave the hydrogenated products whose optical yields were found to be good (ca. 90% ee). A new type of bidentate ligands, (2-amino-1-phosphino)cycloalkanes were synthesized. In chapter 2, a versatile reagent, (2-diethoxyphosphinylcyclobutyl)triphenylphosphonium salt was developed. The double Wittig reaction using this salt and various carbonyl reagents produced 1,2-bis(ylidene)cyclobutanes in good yields. The 1,2-bis(ylidene)cyclobutanes underwent sequential Diels-Alder reaction with two equiv. of various dienophiles to give functionalized polycyclic compounds. In conclusion, these results can be said to have achieved the initially attempted subjects for this project.