芳基乙酮酸薄荷醇酯的合成及不对称Henry反应

Synthesis and Asymmetric Henry Reaction of Menthyl Arylglyoxylate

以钛酸四乙酯为催化剂,芳基乙酮酸乙酯与天然L-薄荷醇进行酯交换,合成了8个含手性基团的芳基乙酮酸薄荷醇酯;在手性基团的立体选择性控制下,芳基乙酮酸薄荷醇酯与硝基甲烷进行不对称Henry反应,合成了7个(2R)-2-羟基-2-芳基-3-硝基丙酸薄荷醇酯新化合物,用IR,1H NMR,13C NMR,MS和元素分析表征了化合物结构.用高效液相色谱经手性柱分析了不对称反应效果,缩合反应的非对映体过量在46.5%～64.2%之间,表明可以通过立体选择性控制产物构型.

In the presence of titanium（ Ⅳ ） tetraethoxide, eight chiral menthyl arylglyoxylates were prepared by transesterification of ethyl arylglyoxylates and the natural （1 R, 2S ,SR）- （ - ）-menthol. Seven new menthyl （2R）-2-hydroxy-2-aryl-3-nitropropionates were synthesized by the Henry reaction of menthyl arlglyoxylates and nitromethane. The structures of the products were characterized by IR, 1H NMR, 13C NMR spectroscopy, MS and elemental analysis. The diastereoselectivities were analyzed by HPLC with chiral column. The diastereomeric excess（ d. e. ） of the condensation reactions were between 46.5%--64. 2%, achieve diastereoselectivities control to the structure.