Gallagher Eva T, Grayson David H
Centre for Synthesis and Chemical Biology, Department of Chemistry, Trinity College, Dublin 2, Ireland.
Org Biomol Chem. 2003 Apr 21;1(8):1374-81. doi: 10.1039/b300925b.
(E)-3-Chloro-1-phenylsulfonylprop-1-ene and its iodo- and bromo-analogues, (Z)-1-iodo-3-phenylsulfonylprop-1-ene and (Z)-1-bromo-3-phenylsulfonylprop-1-ene, have each been successfully converted into lithiated carbanions which react regioselectively with aromatic aldehydes to give gamma-alkylated products whose nature depends upon the halogen substituent: the chloro-sulfones yield (2Z)-1-aryl-2-chloro-4-phenylsulfonylbut-2-en-1-ols but the bromo- and iodo-derivatives behave differently, yielding (1E)-trans-4-aryl-3,4-epoxy-1-phenylsulfonylbut-1-enes. In sharp contrast, the same lithiated sulfones react with aliphatic aldehydes to give anti-configured beta-hydroxysulfones which are formed via diastereoselective alpha-alkylation reactions.
（E）-3-氯-1-苯基磺酰基-1-丙烯及其碘代和溴代类似物，（Z）-1-碘-3-苯基磺酰基-1-丙烯和（Z）-1-溴-3-苯基磺酰基-1-丙烯，均已成功转化为锂化碳负离子，这些负离子与芳香醛发生区域选择性反应，生成γ-烷基化产物，其性质取决于卤素取代基：氯代砜生成（2Z）-1-芳基-2-氯-4-苯基磺酰基-2-丁烯-1-醇，但溴代和碘代衍生物的行为不同，生成（1E）-反式-4-芳基-3,4-环氧-1-苯基磺酰基-1-丁烯。形成鲜明对比的是，相同的锂化砜与脂肪醛反应，生成通过非对映选择性α-烷基化反应形成的反式构型的β-羟基砜。
