Wang Tongdao, Liu Lei, Grimme Stefan, Daniliuc Constantin G, Kehr Gerald, Erker Gerhard
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstraße 4, 53115, Bonn, Germany.
Chem Asian J. 2016 May 6;11(9):1394-9. doi: 10.1002/asia.201600060. Epub 2016 Mar 24.
Twofold hydroboration of N,N-diallylaniline with the C6 F5 BH2 ⋅SMe2 reagent gave the respective hetero-bicyclo[3.3.0]octane and hetero-methylbicyclo[3.2.0]heptane compounds 4 and 5 as the major products, both showing strong internal N-B amine Lewis base/borane Lewis acid adduct formation. A DFT analysis indicated their formation (and that of a small amount of several isomeric five-membered heterocyclic products) under thermodynamic control. Compound 5 underwent fragmentation with propene liberation to form compound 7 with a formal N=B bond at 100 °C. This product was also obtained from the isomer 4 at much higher temperature (300 °C).
N,N-二烯丙基苯胺与C6F5BH2·SMe2试剂进行双重硼氢化反应，得到相应的杂双环[3.3.0]辛烷和杂甲基双环[3.2.0]庚烷化合物4和5作为主要产物，二者均显示出强烈的内部N-B胺路易斯碱/硼烷路易斯酸加合物形成。密度泛函理论（DFT）分析表明它们（以及少量几种异构五元杂环产物）是在热力学控制下形成的。化合物5在100 °C下发生断裂并释放出丙烯，形成具有形式上N=B键的化合物7。该产物在更高温度（300 °C）下也可从异构体4获得。
