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- Title
Rh<sup>III</sup>‐Catalyzed Functionalization of closo‐Dodecaborates by Selective B−H Activation: Bypassing Competitive C−H Activation.
- Authors
Zhang, Yuanbin; Wang, Tao; Wang, Lingyao; Sun, Yuji; Lin, Furong; Liu, Jiyong; Duttwyler, Simon
- Abstract
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. 2B or not 2B: Rhodium(III)‐catalyzed B−H alkenylation–cyclization and alkylation–cyclization of closo‐dodecaborate amides have been achieved by using acetylenes and alkenes as the coupling reagents. The reactions occur selectively at B−H positions in the presence of C−H bonds prone to competitive cyclometalation. New boron clusters with B−C(sp2) and B−C(sp3) bonds are obtained in a mild one‐pot process.
- Subjects
RHODIUM catalysts; ACTIVATION (Chemistry); BORON; CHEMOSELECTIVITY; CHEMICAL amplification
- Publication
Chemistry - A European Journal, 2018, Vol 24, Issue 59, p15812
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201803455