Desymmetrization of Vicinal Bis(boronic) Esters by Enantioselective Suzuki-Miyaura Cross-Coupling Reaction.
Desymmetrization of Vicinal Bis(boronic) Esters by Enantioselective Suzuki-Miyaura Cross-Coupling Reaction.
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DOI：
10.1021/jacs.3c01571
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发表时间：
2023-04
影响因子：
15
通讯作者：
Mingkai Zhang;Paul S Lee;C. Allais;R. Singer;J. Morken
中科院分区：
文献类型：
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作者：
Mingkai Zhang;Paul S Lee;C. Allais;R. Singer;J. Morken
描述了适用于内消旋 1,2-二硼基环烷烃的对映选择性催化 Suzuki-Miyaura 反应的发展。该反应为获得对映体富集的取代碳环和杂环提供了模块化途径，同时保留了合成上通用的硼酸酯。通过适当构建的底物，可以以简单的方式生成带有额外立体中心和完全取代的碳原子的化合物。初步的机理实验表明，底物活化是由金属转移步骤中邻位硼酸酯的协同作用引起的。
The development of an enantioselective catalytic Suzuki-Miyaura reaction that applies to meso 1,2-diborylcycloalkanes is described. This reaction provides a modular route to enantiomerically enriched substituted carbocycles and heterocycles that retain a synthetically versatile boronic ester. With appropriately constructed substrates, compounds bearing additional stereogenic centers and fully substituted carbon atoms can be generated in a straightforward fashion. Preliminary mechanistic experiments suggest that substrate activation arises from the cooperative effect of vicinal boronic esters during the transmetalation step.