He Yicheng, Yan Biwei, Ma Cheng, Ni Shaofei, Guo Wusheng
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University Yanxiang Road 99 Xi'an 710045 China
Department of Chemistry, Shantou University Shantou 515063 China.
Chem Sci. 2024 Nov 26;16(2):834-839. doi: 10.1039/d4sc06849a. eCollection 2025 Jan 2.
The first Ni-catalyzed asymmetric decarboxylative strategy for the construction of carbocycles with contiguous quaternary all-carbon stereocenters is reported. The key to the success of these reactions is the utilization of rationally designed allenylic methylene cyclic carbonates as substrates with Ni catalysis. The floppy allenylic group exerts unique electronic properties on the carbonate, which allows further asymmetric nucleophilic annulations with alkenes. These reactions can be performed at room temperature and feature wide functional group tolerance with excellent asymmetric induction that is typically >94% ee. The mechanistic insights imply that this conceptually new chemistry is completely different from previous reports on the catalytic transformation of cyclic carbonates, and thus, it offers an inventive novel methodology to create complex enantio-enriched molecules.
报道了首例用于构建具有相邻全碳季碳立体中心的碳环的镍催化不对称脱羧策略。这些反应成功的关键在于利用合理设计的烯丙基亚甲基环状碳酸酯作为镍催化的底物。柔软的烯丙基对碳酸酯具有独特的电子性质，这使得其能够与烯烃进一步进行不对称亲核环化反应。这些反应可以在室温下进行，具有广泛的官能团耐受性和优异的不对称诱导效果，对映体过量值（ee）通常>94%。机理研究表明，这种概念上全新的化学与先前关于环状碳酸酯催化转化的报道完全不同，因此，它为构建复杂的对映体富集分子提供了一种新颖的创新方法。
