Ariza Xavier, Garcia Jordi, Georges Yohan, Vicente Mar
Departament de Química Orgànica, Universitat de Barcelona, Martí i Franquès 1, 08028 Barcelona, Spain.
Org Lett. 2006 Sep 28;8(20):4501-4. doi: 10.1021/ol0616539.
(R)- or (S)-1-phenylprop-2-ynyl acetate was added stereoselectively to aldehydes to afford 4-hydroxy-1-phenylalk-2-ynyl acetates. The transformation of such adducts into the corresponding allylic 1,4-diacetates allowed a highly efficient transfer of chirality from C1 to C3 by a regio- and stereoselective [3,3]-sigmatropic rearrangement. The obtained unsaturated 1,2-diacetates were useful synthetic intermediates whose double bond and/or phenyl group were transformed in different aldehydes, acids, or esters.
将（R）-或（S）-1-苯基丙-2-炔基乙酸酯立体选择性地添加到醛中，得到4-羟基-1-苯基烷-2-炔基乙酸酯。通过区域和立体选择性的[3,3] - 迁移重排，将此类加合物转化为相应的烯丙基1,4-二乙酸酯，实现了手性从C1到C3的高效转移。所得到的不饱和1,2-二乙酸酯是有用的合成中间体，其双键和/或苯基可转化为不同的醛、酸或酯。
