Structural Elucidation and Synthetic Application of Organozinc reagents with Pronounced Nucleophilic Reactivity

(1)提出了不对称取代酮的合成新反应。在室温下，在1atm的一氧化碳浓度下，通过钯的催化，烯丙基苯甲酸酯、一氧化碳和有机化合物的三组分连接反应进行反应。相对于烯丙基部分，反应表现出相当典型的区域选择性（α和γ -）和立体选择性（构型反转）。该反应适用于结构多样的烯丙基底物（苯甲酸盐、磷酸盐）与有机锌(IZn (CH_2)_n X，X=CO_2 Et， CN；碘化辛基锌（二乙基锌）(2)开发了pi-烯丙基钯的测定新方法。二乙基锌经烯丙基-乙基金属转化反应处理后，可清洁地合成pi-烯丙基钯。该反应对钯具有催化作用，苯甲酸烯丙酯、羰基化合物（醛、酮、酯）、二乙基锌和四苯基（三苯基膦）钯的混合物以相当高的收率生成相应的均烯丙醇。与烯丙基卤化锌的烯丙基化反应显示出高的区域选择性和立体选择性。

(1) The new synthetic reaction of unsymmetrically substituted ketones was developed. The reaction proceeds via the three-component connection reaction of allylic benzoates, carbon monoxide, and organozincs by the catalysis of palladium at room temperature under 1 atm of carbon monoxide. The reaction shows quite characteristic regio (alpha-and gamma-) -and stereoselectivity (inversion of configuration) with respect to the allylic moiety. The reaction is applicable to the combination of a wide structural variety of allylic substrates (benzoates, phosphates) and organozincs (IZn (CH_2)_n X,X=CO_2 Et, CN ; octylzinc iodide, diethylzinc).(2) The new method of umpolung of pi-allylpalladium was developed. The umpolung of pi-allylpalladium takes place cleanly by treatment with diethylzinc via allyl-ethyl transmetallation reaction. The reaction can be catalytic with respect to palladium and the mixture of an allyl benzoate, a carbonyl compound (aldehyde, ketone, ester), diethylzinc, and tetrakis (triphenylphosphine) palladium provides the corresponding homoallyl alcohol in quite high yield. The reaction displays high regio-and stereoselectivity, having been not observed for the allylation with allyzinc halides.