A Pd/Cu catalyzed stereodivergent desymmetrization of unsubstituted allylic dicarboxylates was developed and the corresponding products could be generated in excellent yields with good stereoselectivity. Notably, the reaction favored branch-selectivity. Large scale experiment and the transformations of products indicated the potential utility of this reaction. In addition, computational studies revealed that the greater electrophilicity of branch carbon in the π-allyl-Pd intermediate and the weak noncovalent interactions among the substrates and the catalysts contributed to the high branch-selectivity of this reaction.

中文翻译：

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通过分支选择性 Pd/Cu 催化烯丙基取代对简单二羧酸盐进行立体发散去对称化

开发了一种 Pd/Cu 催化的未取代的烯丙基二羧酸酯的立体发散去对称化，并且可以以优异的收率和良好的立体选择性生成相应的产物。值得注意的是，该反应有利于分支选择性。大规模实验和产物的转化表明了该反应的潜在用途。此外，计算研究表明，π-烯丙基-Pd中间体中支链碳的更大亲电性以及底物和催化剂之间较弱的非共价相互作用有助于该反应的高支链选择性。