CATALYTIC ASYMMETRIC-SYNTHESIS OF BETA-HYDROXY KETONES BY PALLADIUM-CATALYZED ASYMMETRIC 1,4-DISILYLATION OF ALPHA,BETA-UNSATURATED KETONES
CATALYTIC ASYMMETRIC-SYNTHESIS OF BETA-HYDROXY KETONES BY PALLADIUM-CATALYZED ASYMMETRIC 1,4-DISILYLATION OF ALPHA,BETA-UNSATURATED KETONES
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DOI：
10.1016/s0040-4020(01)80758-4
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发表时间：
1994-01-10
期刊：
影响因子：
2.1
通讯作者：
ITO, Y
中科院分区：
文献类型：
--
作者：
MATSUMOTO, Y;HAYASHI, T;ITO, Y
在膦钯催化剂存在下，α，β-不饱和酮与1，1-二氯-1-苯基-2，2，2-三甲基二硅烷进行1，4-二硅烷基化反应。在二氯[（R）-2，2 '-双（二苯基膦基）-1，1'-联萘]钯（II）作为催化剂（0.5mol%）的二甲硅烷基化反应中观察到高的对映选择性（高达92%）。二硅烷基化产物1-（三甲基硅氧基）-3-（二氯苯基硅烷基）丙烯很容易转化为光学活性的α-未取代或反α-取代的β-（苯基二甲基硅烷基）酮，其氧化得到相应的光学活性β-羟基酮，产率高。
1,4-Disilylation of alpha,beta-unsaturated ketones with 1.1-dichloro-1-phenyl-2,2,2-trimethyldisilane proceeded in the presence of phosphine-palladium catalysts in benzene. High enantioselectivity (up to 92%) was observed in the disilylation with dichloro[(R)-2,2'-bis(diphenylphosphino)- 1,1'-binaphthyl]palladium(II) as a catalyst (0.5 mol %). The disilylation products, 1-(trimethylsilyloxy)-3- (dichlorophenylsilyl)propenes, were readily converted into optically active alpha-unsubstituted or anti alpha-substituted beta-(phenyldimethylsilyl) ketones, the oxidation of which gave the corresponding optically active beta-hydroxy ketones in high yields.