Living And Enantiomer-Selective Polymerization Of Chiral Allene Initiated By Ni Complex Containing Chiral Phosphine

The wonderful relationship between the biological activity and specific structure of chiral compounds has always been the focus of scientists.Enantiomer-selective polymerization means that one enantiomer is preferentially polymerized to obtain optically active polymer and unreacted monomer.We tried to explore the possibility of enantiomer selective polymerization for L-and D-N-（1-（dodecylamino）-1-oxopropan-2-yl）-4-（propa-1,2-dien-1-yloxy）-benzamide（L-1 and D-1）by using allylnickel complex containing chiral phosphine.We used（S）-（-）-2,2’-Bis（diphenylphosphino）-1,1’-binaphthalene（（S）-BINAP）、（R）-（2’-methoxy[1,1’-binaphthalen]-2-yl）diphenyl-phosphine（（R）-POM）、[S（R）]-N-[（1S）-2-（Diphenylphosphino）-1-phenylethyl]-2-methyl-2-propanesul finamide（Xiao-Phos）as the ligand to prepared the allylnickel complex.Three of these catalysts are capable of catalyzing the polymerization of allene in living manner.In the kinetics study of the polymerization of L-1 and D-1,the polymerization rate of L-1 is approximately 1.9 times that of D-1 by using Xiao-Phos ligand catalyst.This catalyst has enantiomer-selectivity for the polymerization of chiral allene derivative monomer.In the copolymerization of rac-1 by using poly-L-1₅₀ as the macroinitator,all the copolymer and the unreacted monomer were optical active.We can see that the slight changes in the surrounding environment of the coordination metal have a huge impact on the polymerization.The use of chiral ligand is an effective method to achieve enantiomer-selective polymerization.The role of the ligand is crucial.The use of Xiao-Phos can achieve enantiomer-selective polymerization of chiral allene monomers.