Novikov Roman A, Borisov Denis D, Denisov Dmitry A, Novikov Maxim A, Potapov Konstantin V, Tkachev Yaroslav V, Tomilov Yury V
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation.
Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, 32 Vavilov st., 119991, Moscow, Russian Federation.
Nat Commun. 2024 Sep 14;15(1):8073. doi: 10.1038/s41467-024-51237-5.
The direct C-H activation of inert C(sp)-H bonds in a hydrocarbon chain has been a very attractive target in organic synthesis for many decades. Among all the variety of processes, those driven by vinyl carbocations are quite scarce thus far, and it is hard to control for unstabilized vinyl cations. In this study, we designed a double C(sp)-H functionalization of unactivated alkyl CH groups to produce a totally substituted quaternary carbon stereocenter via insertion of vinyl carbocations. These processes represent complicated reaction cascades with high molecular complexity controlled by the cooperative action of Ga(III) salts & GaHal anions and allow one-step deep poly-functionalization of simple CH substrates to be performed. In practice, this concept was initially implemented with simple starting compounds such as alkyl acetylenes and activated cyclopropanes, alkenes, or cyclobutanes to construct norbornane, cyclopentatetralin, and other important skeletons.
几十年来，烃链中惰性C(sp)-H键的直接C-H活化一直是有机合成中一个非常有吸引力的目标。在所有各种各样的过程中，由乙烯基碳正离子驱动的过程迄今为止相当稀少，并且难以控制不稳定的乙烯基碳正离子。在本研究中，我们设计了未活化烷基CH基团的双C(sp)-H官能化反应，通过乙烯基碳正离子的插入生成完全取代的季碳立体中心。这些过程代表了具有高分子复杂性的复杂反应级联，由Ga(III)盐和GaHal阴离子的协同作用控制，并允许对简单的CH底物进行一步深度多官能化。实际上，这一概念最初是用简单的起始化合物如烷基乙炔和活化的环丙烷、烯烃或环丁烷来实现的，以构建降冰片烷、环戊并四氢化萘和其他重要骨架。
