The closo‐dodecaborate dianion is a fundamental icosahedral boron cage with 12 identical B−H vertices. The chemistry and applications of boron clusters have inspired researchers ever since their discovery several decades ago, and the selective modification of the cage positions has remained a major synthetic challenge. A rhodium(III)‐catalyzed B−H functionalization–cyclization cascade of closo‐dodecaborate amides is reported. The transformations occur chemoselectively at B−H positions in the presence of C−H bonds prone to competitive cyclometalation. Previously inaccessible cage derivatives with B−C(sp²) and B−C(sp³) bonds as well as a fused diboraoxazole ring are obtained in a one‐pot process. The reactions proceed under mild conditions and exhibit complete cage regioselectivity with broad functional group tolerance. These cluster derivatives enable a largely extended investigation of the application of anionic boron clusters in research areas such as photoluminescent materials and medicinal chemistry.

中文翻译：

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RhIII通过选择性的B-H活化催化Closo-Dodecaborates的功能化：绕过竞争的C-H活化

所述闭合碳-dodecaborate二价阴离子是一个根本性的二十面体硼笼12相同B-H顶点。硼团簇的化学和应用自几十年前被发现以来一直激励着研究人员，笼子位置的选择性修饰仍然是一个主要的合成挑战。的铑（III）催化的B-H官能化的环化级联闭合碳报道-dodecaborate酰胺。在存在容易发生竞争性环金属化的CH键的情况下，该化学选择性地在NH位发生转变。以前无法访问的具有BC（sp ²）和BC（sp ^3的笼子导数）键以及一个稠合的二硼恶唑环是通过一锅法获得的。反应在温和的条件下进行，并表现出完全的笼区域选择性和宽泛的官能团耐受性。这些簇衍生物使得能够广泛地研究阴离子硼簇在研究领域中的应用，例如光致发光材料和药物化学。