Expanding the Scope of Palladium-Catalyzed B–N Cross-Coupling Chemistry in Carboranes,Organometallics

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Expanding the Scope of Palladium-Catalyzed B–N Cross-Coupling Chemistry in Carboranes
Organometallics ( IF 2.5 ) Pub Date : 2020-11-26 , DOI: 10.1021/acs.organomet.0c00576
Xin Mu ₁ , Morgan Hopp ₁ , Rafal M Dziedzic ₁ , Mary A Waddington ₁ , Arnold L Rheingold ₂ , Ellen M Sletten ₁ , Jonathan C Axtell ₁ , Alexander M Spokoyny ₁

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Over the past several years, a number of strategies for the functionalization of dicarba-closo-dodecaboranes (carboranes) have emerged. Despite these developments, B–N bond formation on the carborane scaffold remains a challenge due to the propensity of strong nucleophiles to partially deboronate the parent closo-carborane cluster into the corresponding nido form. Here we show that azide, sulfonamide, cyanate, and phosphoramidate nucleophiles can be straightforwardly cross-coupled onto the B(9) vertices of the o- and m-carborane core from readily accessible precursors without significant deboronation byproducts, laying the groundwork for further study into the utility and properties of these new B-aminated carborane species. We further showcase the select reactivity of the installed functional groups, highlighting some unique features stemming from the combination of the electron-donating B(9) position and the large steric profile of the B-connected carborane substituent.

中文翻译：

扩大碳硼烷中钯催化 B-N 交叉偶联化学的范围

在过去的几年中，许多用于dicarba-的功能化战略闭合碳-dodecaboranes（碳硼烷）已经出现。尽管有这些进展，对碳硼烷骨架B-N键的形成仍然是一个挑战，由于强的亲核试剂的倾向部分deboronate父闭合碳-carborane簇成相应的巢式形式。在这里，我们表明叠氮化物、磺酰胺、氰酸盐和氨基磷酸酯亲核试剂可以直接交叉耦合到o - 和m的 B(9) 顶点-碳硼烷核心来自易于获得的前体，没有显着的脱硼副产物，为进一步研究这些新的 B-胺化碳硼烷物种的效用和性质奠定了基础。我们进一步展示了安装的官能团的选择性反应性，突出了一些独特的特征，这些特征源于供电子 B(9) 位置和 B 连接碳硼烷取代基的大空间分布的组合。

更新日期：2020-12-14

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