(Z)-β-芳基硬脂基乙烯基膦酸酯和(Z)-β-芳基硬脂基乙烯基砜是通过对1-炔基膦酸酯和1-炔基砜进行高度立体选择性的抗氢纤化作用合成的。这些化合物的构型通过1 H NMR光谱或NOESY实验以及X射线衍射分析进行表征。通过芳基碲酸钠与(E)-2-碘乙烯基砜的反应,得到(E)-β-芳基碲基乙烯基砜,从而证实了上述抗加氢碲化的立体化学。当炔烃与二芳基二碲化物和芳基亚磺酸钠的串联反应在AcOH / H2O(4/1)中进行时,一步即可以高收率获得相应的(E)-β-芳基tellurovinyl砜。该反应是高度区域选择性和立体选择性的,并且通过使用芳基亚磺酸盐作为磺酰基自由基前体和二芳基二碲化物作为自由基受体来进行。(E)-1-碘-2-芳基碲代烯烃可通过将ArTeI与末端炔在THF中反加成而获得。化合物17b的立体化学也通过X射线衍射分析确定。
Stereoselective synthesis of (E)-α-aryltellurenylvinylsilanes via hydromagnesiation reaction of alkynylsilanes
作者:Mingzhong Cai、Wenyan Hao、Hong Zhao、Jun Xia
DOI:10.1016/j.jorganchem.2004.02.027
日期:2004.5
(E)-α-Aryltellurenylvinylsilanes have been synthesized stereoselectivelyvia the hydromagnesiation of alkynylsilanes, followed by the reaction with aryltellurenyl iodides. (E)-α-Aryltellurenylvinylsilanes can undergo the cross coupling reaction with Grignard reagents in the presence of Ni(PPh3)2Cl2 catalyst to afford (Z)-1,2-disubstituted vinylsilanes in good yields.