The C[BOND]H Activation/1,3-Diyne Strategy: Highly Selective Direct Synthesis of Diverse Bisheterocycles by RhIII Catalysis


  • We thank Prof. Zhuangzhi Shi, Prof. Honggen Wang, Dr. Dongbing Zhao, Dr. Mélissa Boultadakis-Arapinis, Dr. Karl D. Collins, and Nils Schröder for helpful discussions. We are very grateful to the Alexander von Humboldt Foundation (D.G.Y.), São Paulo Research Foundation (grant 2013/14209-9, F.d.A.), the European Research Council (ERC) under the European Community’s Seventh Framework Program (FP7 2007–2013)/ERC grant agreement no. 25936, and the DFG (Leibniz award; F.G.) for generous financial support.


The reactivity and selectivity of 1,3-diynes in transition-metal-catalyzed C[BOND]H activation is exploited to quickly assemble diverse polysubstituted bisheterocycles, which are highly important but difficult to access. By using the C[BOND]H activation/1,3-diyne strategy, we overcame the challenges of selectivity (chemo-, regio-, and mono-/diannulation) and constructed seven kinds of adjacent bisheterocycles through the formation of four strategic bonds with high efficiency and high selectivity.