Studies on the Synthesis and the Application of New Functionalized Phosphines

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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.