In this work, we described a remote desymmetrization reaction in which cesium carboxylate, in the presence of bisguanidinium as catalyst, was added to (cis)-α,α′-dibromocyclohexanone to access 6-oxocyclohex-1-enyl ester via a 1,2-acyl shift in a highly enantioselective fashion. In this process, the carboxylate initiated a nucleophilic attack, and then a keto-enol tautomerism led to a 1,2-acyl shift to the neighboring alcohol. Key intermediates were isolated and determined using single-crystal X-ray crystallography. The remote desymmetrization that includes stepwise S_N2 and intramolecular acyl transfer was proposed and was further supported using computational studies. Finally, it was successfully applied to a tropinone derivative, realizing carbonyl chain walking efficiently.

在这项工作中，我们描述了一种远程去对称反应，其中在双胍作为催化剂的存在下，将羧酸铯添加到(顺式)-α,α'-二溴环己酮中，通过1,以高度对映选择性方式进行 2-酰基转移。在此过程中，羧酸酯引发亲核攻击，然后酮-烯醇互变异构导致 1,2-酰基转移到邻近的醇。使用单晶 X 射线晶体学分离并测定了关键中间体。提出了包括逐步 S _N 2 和分子内酰基转移的远程去对称化，并通过计算研究得到了进一步支持。最后成功应用于托品酮衍生物，实现了高效的羰基链行走。