Mei Ruhuai, Wang Hui, Warratz Svenja, Macgregor Stuart A, Ackermann Lutz
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany.
Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK.
Chemistry. 2016 May 10;22(20):6759-63. doi: 10.1002/chem.201601101. Epub 2016 Apr 8.
Cp*-free cobalt-catalyzed alkyne annulations by C-H/N-H functionalizations were accomplished with molecular O2 as the sole oxidant. The user-friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C-H cobaltation, providing among others step-economical access to the anticancer topoisomerase-I inhibitor 21,22-dimethoxyrosettacin. DFT calculations suggest that electronic effects control the regioselectivity of the alkyne insertion step.
通过C-H/N-H官能团化实现的无茂环钴催化炔烃环化反应以分子氧作为唯一氧化剂完成。这种用户友好的氧化酶策略通过动力学相关的C-H钴化反应，对各种内炔和端炔均证明是可行的，尤其提供了一种步骤经济的方法来合成抗癌拓扑异构酶-I抑制剂21,22-二甲氧基玫瑰树碱。密度泛函理论计算表明，电子效应控制着炔烃插入步骤的区域选择性。
