Ye Jialin, Liao Yang, Huang Hao, Liu Yang, Fang Dongmei, Wang Min, Hu Lianrui, Liao Jian
College of Chemical Engineering, Sichuan University Chengdu 610065 China.
Natural Products Research Center, Chengdu Institute of Biology, Chinese Academy of Sciences Chengdu 610041 China
Chem Sci. 2020 Dec 22;12(8):3032-3038. doi: 10.1039/d0sc05425a.
An enantioselective 1,4-borylstannation of 1,3-enynes employed a chiral sulfoxide phosphine ()/Cu complex as a catalyst, and the desired products, chiral allenylstannes, were first synthesized by asymmetric catalysis with satisfactory yields and enantioselectivies. In this protocol, a catalytic amount of additive, a halogenated salt, plays a crucial role in the success. Control experiments and theoretical studies disclosed that the four-membered ring transmetallation transition states which were stabilized by a halide anion are the key to yields and stereochemical outcomes.
使用手性亚砜膦（）/铜配合物作为催化剂，对1,3-烯炔进行对映选择性1,4-硼锡化反应，首次通过不对称催化合成了所需产物手性烯丙基锡，产率和对映选择性令人满意。在该反应中，催化量的添加剂卤化盐对反应成功起着关键作用。对照实验和理论研究表明，由卤化物阴离子稳定的四元环转金属化过渡态是产率和立体化学结果的关键。
