Chen Chaohuang, Daniliuc Constantin G, Kehr Gerald, Erker Gerhard
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2021 Sep 1;60(36):19905-19911. doi: 10.1002/anie.202106724. Epub 2021 Aug 3.
The synthesis of element-carbon double bonds is of great importance for the development and understanding of reactive π-bonded systems in chemistry. The seven-membered heterocyclic system 4 b is readily made by internal C-H activation at a pendent isopropyl methyl group of the respective [(IPr)C F BH] borenium ion. Subsequent deprotonation with the IMes carbene gives the neutral cyclic boraalkene system 5 b. The B=C double bond in compound 5 b adds carbon dioxide, CS , sulfur dioxide, phenyl isocyanate, an acetylenic ester or two NO molecules to give the corresponding four-membered ring annulated heterocycles. With sulfur or selenium 5 b gives the respective three-membered ring systems. N O reacts with 5 b to give a mixture of the related oxaborirane 18 and a unique [B]OH containing diazoalkane product 19.
元素 - 碳双键的合成对于化学中活性π键体系的发展和理解具有重要意义。七元杂环体系4 b可通过相应的[(IPr)C F BH]硼正离子的侧链异丙基甲基上的内部C - H活化轻松制得。随后用IMes卡宾进行去质子化得到中性环状硼烯烃体系5 b。化合物5 b中的B = C双键与二氧化碳、CS、二氧化硫、苯基异氰酸酯、炔酯或两个NO分子加成，得到相应的稠合四元环杂环。与硫或硒反应时，5 b生成相应的三元环体系。N O与5 b反应生成相关的氧硼杂环丁烷18和独特的含[B]OH重氮烷产物19的混合物。
