正丁基锂在-78℃攫取(α-烷氧羰基)乙基膦酸二乙酯(1)的活泼氢得到碳负离子2,其进攻三氟醋酸酐产生三氟乙酰基膦酸酯(3);不经过分离,直接用Grignard试剂进攻三氟乙酰基膦酸酯(3),由HWE反应选择性地合成了以Z-式为主的β-三氟甲基-α-甲基-α、β-不饱和酸酯(4),按兰计,三步反应的总收率为59%-92%,Z-构型反应产物是主要产物。
Diethyl (α-alkoxycarbonylethyl)phosphonate (1) was treated with n-butyllithium in tetrahydrofuran at -78℃. The resulting carbanion 2 reacted with trifluoroacetic acid anhydride to afford trifluoroacylated phosphonate intermediate (3), and without isolation, 3 was attacked by Grignard reagents via HWE reaction giving β- trifluoromethylated-α-methyl-α,β-unsaturated esters (4) in totally 59%-92% yields with dominantly Z- stereoselectivity.