Yan Zhongfei, Yuan Xiang-Ai, Zhao Yue, Zhu Chengjian, Xie Jin
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, 273165, China.
Angew Chem Int Ed Engl. 2018 Sep 24;57(39):12906-12910. doi: 10.1002/anie.201807851. Epub 2018 Sep 5.
The transition-metal-catalyzed selective hydroarylation of unsymmetrical alkynes represents the state-of-art in organic chemistry, and still mainly relies on the use of precious late-transition-metal catalysts. Reported herein is an unprecedented Mn -catalyzed hydroarylation of unsymmetrical 1,3-diyne alcohols with commercially available arylboronic acids with predictive selectivity. This method addresses the challenges in regio-, stereo-, and chemoselectivity. It offers a general, convenient and practical strategy for the modular synthesis of multisubstituted Z-configurated conjugated enynes. This protocol is distinguished by its operational simplicity, complete selectivity, excellent functional-group compatibility, and gram-scale potential. A dimeric Mn species, Mn (CO) Br , was proven to be a much more efficient catalyst precursor than Mn(CO) Br.
过渡金属催化的不对称炔烃选择性氢芳基化反应代表了有机化学的前沿水平，且仍主要依赖于使用昂贵的后过渡金属催化剂。本文报道了一种前所未有的锰催化不对称1,3-二炔醇与市售芳基硼酸的氢芳基化反应，具有可预测的选择性。该方法解决了区域选择性、立体选择性和化学选择性方面的挑战。它为多取代Z-构型共轭烯炔的模块化合成提供了一种通用、便捷且实用的策略。该方案具有操作简单、选择性完全、官能团兼容性优异以及克级规模制备潜力等特点。已证明二聚体锰物种Mn(CO)Br是一种比Mn(CO)Br更高效的催化剂前体。
