Li Bao-Sheng, Wang Yuhuang, Jin Zhichao, Zheng Pengcheng, Ganguly Rakesh, Chi Yonggui Robin
Nanyang Technological University, Division of Chemistry &Biological Chemistry, School of Physical &Mathematical Sciences, Singapore, 637371, Singapore.
Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Huaxi District, Guiyang 550025, China.
Nat Commun. 2015 Feb 5;6:6207. doi: 10.1038/ncomms7207.
The activation of carbon-carbon (C-C) bonds is an effective strategy in building functional molecules. The C-C bond activation is typically accomplished via metal catalysis, with which high levels of enantioselectivity are difficult to achieve due to high reactivity of metal catalysts and the metal-bound intermediates. It remains largely unexplored to use organocatalysis for C-C bond activation. Here we describe an organocatalytic activation of C-C bonds through the addition of an NHC to a ketone moiety that initiates a C-C single bond cleavage as a key step to generate an NHC-bound intermediate for chemo- and stereo-selective reactions. This reaction constitutes an asymmetric functionalization of cyclobutenones using organocatalysts via a C-C bond activation process. Structurally diverse and multicyclic compounds could be obtained with high optical purities via an atom and redox economic process.
碳-碳（C-C）键的活化是构建功能分子的有效策略。C-C键的活化通常通过金属催化来实现，然而，由于金属催化剂和金属配位中间体的高反应性，很难实现高水平的对映选择性。利用有机催化进行C-C键活化在很大程度上仍未得到探索。在此，我们描述了一种通过将氮杂环卡宾（NHC）加成到酮部分来实现C-C键的有机催化活化，该过程引发C-C单键断裂作为关键步骤，以生成用于化学和立体选择性反应的NHC配位中间体。该反应通过C-C键活化过程构成了使用有机催化剂对环丁烯酮的不对称官能化。通过原子和氧化还原经济过程，可以获得具有高光学纯度的结构多样的多环化合物。
