Wang Fei, Wang Dinghai, Zhou Yu, Liang Ling, Lu Ronghua, Chen Pinhong, Lin Zhenyang, Liu Guosheng
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Angew Chem Int Ed Engl. 2018 Jun 11;57(24):7140-7145. doi: 10.1002/anie.201803668. Epub 2018 May 14.
A ligand-controlled system that enables regioselective trifluoromethylcyanation of 1,3-enynes has been identified, which provides access to a variety of CF -containing tri- and tetrasubstituted allenyl nitriles. We disclose that the involved propargylic radicals can be selectively trapped by (Box)Cu cyanide, while the tautomerized allenyl radicals are trapped by (phen)Cu cyanide (Box= bisoxazoline, phen=phenanthroline). In addition, the reaction features broad substrate scope and excellent functional group compatibility. Moreover, this protocol represents a novel regioselectivity-tunable functionalization of 1,3-enynes via radicals, which we believe will have great implications for the development of catalytic systems for selectivity control in radical and organometallic chemistry.
已发现一种配体控制的体系，该体系能实现1,3-烯炔的区域选择性三氟甲基氰化反应，从而可得到多种含CF的三取代和四取代丙二烯腈。我们揭示，所涉及的炔丙基自由基可被(Box)Cu氰化物选择性捕获，而异构化后的丙二烯基自由基则被(phen)Cu氰化物捕获（Box = 双恶唑啉，phen = 菲咯啉）。此外，该反应具有广泛的底物范围和出色的官能团兼容性。而且，此方法代表了一种通过自由基对1,3-烯炔进行新型区域选择性可调功能化的方法，我们认为这将对自由基和有机金属化学中选择性控制催化体系的发展具有重要意义。
