Pd Catalyzed Acylphosphine Coupling With Alkyl Halides To Construct C(sp~3)-P(?) Bond

Organophosphorus compounds such as trivalent phosphines that are representatives in this class of phosphines compounds play an very important role in modern organic synthesis and especially as ligands were widely utilized in transition metal catalyzed reactions.Much attention has been paid to developing highly efficient strategies and methodologies on construction of C(sp)-P(III)bond because of the significantly growing demand on the electron-rich phosphine ligands with the development of the research on transition metal catalyzed reaction.The research content of this paper mainly includes the following two parts:Part one:The construction of C-P(?)bond with the electrophilic substitution reaction of acylphosphine and active electrophilic reagents was studied.After designing hypothetical reaction process and then making experiments,it was found that acylphosphine didn't directly react with active electrophilic reagents to afford desired trivalent phosphine compounds and this reaction was prone to producing phosphonium salt due to the over-reaction.The poor results in this part indicated that developing transition metal catalyzed coupling method to construct C(sp3)-P(?)bonds was more feasible and impending.Part two:The coupling reaction of acylphosphine and alkyl halides catalyzed by Pd has been mainly studied.C(sp3)-P(III)bond has been constructed efficiently and selectively with avoiding many problems such as over-reaction and a series of alkyldiphenylphosphine compounds have been synthesized,which were achieved by this Pd catalyzed coupling reaction.It was noted that no product of elimination reaction of primary alkyl halides which was caused by Pd catalyst was not observed.In contrast to the method of construction C(sp3)-P(?)bonds by electrophilic substitution reaction,mild reaction condition was compatible with the group which were not tolerant of strong bases.Thus,the scope of application in this reaction was greatly expended.