通过等叶的B≡N和B≡B三键对丙酮进行单重和双重活化。
Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds.
作者信息
Böhnke Julian, Brückner Tobias, Hermann Alexander, González-Belman Oscar F, Arrowsmith Merle, Jiménez-Halla J Oscar C, Braunschweig Holger
机构信息
Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email:
Institute for Sustainable Chemistry & Catalysis with Boron , Julius-Maximilians-Universität Würzburg , Am Hubland , 97074 Würzburg , Germany.
出版信息
Chem Sci. 2018 Apr 30;9(24):5354-5359. doi: 10.1039/c8sc01249k. eCollection 2018 Jun 28.
B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds induce C-H activation of acetone to yield a (2-propenyloxy)aminoborane and an unsymmetrical 1-(2-propenyloxy)-2-hydrodiborene, respectively. DFT calculations showed that, despite their stark electronic differences, both the B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds activate acetone a similar coordination-deprotonation mechanism. In contrast, the reaction of acetone with a cAAC-supported diboracumulene yielded a unique 1,2,3-oxadiborole, which according to DFT calculations also proceeds an unsymmetrical diborene, followed by intramolecular hydride migration and a second C-H activation of the enolate ligand.
B≡N和B≡B三键分别诱导丙酮的C-H活化，生成(2-丙烯氧基)氨基硼烷和一种不对称的1-(2-丙烯氧基)-2-氢二硼烯。密度泛函理论计算表明，尽管B≡N和B≡B三键在电子性质上存在显著差异，但它们均通过类似的配位-去质子化机制活化丙酮。相比之下，丙酮与一种由环状（烷基）（氨基）卡宾支撑的二硼累积烯烃反应生成了一种独特的1,2,3-氧杂二硼环戊烯，根据密度泛函理论计算，该反应也是先生成一种不对称二硼烯，然后进行分子内氢化物迁移以及烯醇盐配体的第二次C-H活化。
Zotero 插件