含光学活性联二萘酚基团可溶性高分子手性配体的合成及其不对称加成反应

不对称催化是有机化学研究的前沿领域和发展方向．近10年来，手性配体的研究得到了长足的发展，大量的小分子手性配体被报道，其中许多手性配体展示了优异的催化性能．但是由于昂贵的手性配体（金属催化剂）分离、回收和再利用的问题，从而限制了小分子催化剂的应用．因此，解决手性金属催化剂的分离与回收问题是不对称催化研究领域的一个热点问题．为了解决这一关键问题，国内外科学家从负载的角度出发已经成功地发展了众多的研究方法，无机负载法、交联高分子负载法、可溶性高分子负载法、树状大分子负载法等．许多负载的手性金属催化剂已经表现出优异的催化活性和高的对映选择活性．

THE SYNTHESIS OF SOLUBLE POLYMER-SUPPORTED CHIRAL BINOL LIGANDS AND ASYMMETRIC ADDITION REACTIONS

Soluble polymeric chiral binaphthol (BINOL) ligands have been synthesized through copolymerization of 3,3′-bis(hydroxymethyl)-2,2′-bis(methoxymethy leneoxy)-1,1′-binaphthyl,1,6-dihydroxyhexane and 1,4-benzene dicarbonyl chloride followed by deprotection of methoxymethyleneoxy groups by ~iPrOH/HCl,and their application in the enantioselective addition of diethylzinc to benzaldehyde was investigated.All soluble polymeric chiral BINOL ligands were characterized by IR、 ~1H-NMR、GPC and elemental analysis,which clearly demonstrated the formation of polymeric chiral BINOL ligands.These soluble polymeric chiral ligands were found to be effective in the addition of diethylzinc to benzaldehyde either in the presence or in the absence of Ti(O~i Pr)_4 with higher catalytic activities and lower enantioselectivities.In the latter case,the dendritic chiral BINOL ligands showed much higher catalytic activity and a little higher enantioselectivity than BINOLs.