Zhang Xiaoping, Huang Keke, Fu Yanlin, Zhang Ni, Kong Xianglei, Cheng Yuanyuan, Zheng Mingyu, Cheng Yihao, Zhu Tenggao, Fu Bina, Feng Shouhua, Chen Huanwen
Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China University of Technology, Nanchang, 330013, P. R. China.
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, 130012, P. R. China.
Nat Commun. 2024 Jul 13;15(1):5881. doi: 10.1038/s41467-024-49946-y.
Carbon chain elongation (CCE) is normally carried out using either chemical catalysts or bioenzymes. Herein we demonstrate a catalyst-free approach to promote demethylation C-C coupling reactions for advanced CCE constructed with functional groups under ambient conditions. Accelerated by the electric field, two organic cations containing a methyl group (e.g., ketones, acids, and aldehydes) approach each other with such proximity that the energy of the repulsive Coulomb interaction between these two cations exceeds the bond energy of the methyl group. This results in the elimination of a methyl cation and the coupling of the residual carbonyl carbon groups. As confirmed by high-resolution mass spectrometry and isotope-labeling experiments, the C-C coupling reactions (yields up to 76.5%) were commonly observed in the gas phase or liquid phase, for which the mechanism was further studied using molecular dynamics simulations and stationary-point calculations, revealing deep insights and perspectives of chemistry.
碳链延长（CCE）通常使用化学催化剂或生物酶来进行。在此，我们展示了一种无催化剂的方法，用于促进在环境条件下构建具有官能团的高级CCE的去甲基化C-C偶联反应。在电场的加速作用下，两个含有甲基的有机阳离子（如酮、酸和醛）彼此靠近，使得这两个阳离子之间的排斥库仑相互作用能超过甲基的键能。这导致甲基阳离子的消除以及残余羰基碳基团的偶联。通过高分辨率质谱和同位素标记实验证实，C-C偶联反应（产率高达76.5%）在气相或液相中普遍观察到，为此使用分子动力学模拟和驻点计算进一步研究了其机理，揭示了化学的深刻见解和观点。
