Zheng Guangfan, Sun Jiaqiong, Xu Youwei, Zhai Shuailei, Li Xingwei
Key Laboratory of Applied Surface and Colloid Chemistry of MOE School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi'an, 710062, China.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Angew Chem Int Ed Engl. 2019 Apr 1;58(15):5090-5094. doi: 10.1002/anie.201900166. Epub 2019 Mar 12.
Pyridines/pyrimidines are common and effective directing groups in C-H activation. However, they are poorly functionalizable heteroarenes. Reported in this work is Mn-catalyzed dehydrocyanative transannulation between three classes of heteroarenes and propargyl carbonates. The pyridyl/pyrimidyl groups in the heteroarenes initially function as directing groups to enable C-H allenylation; they then undergo intramolecular Diels-Alder/retro-Diels-Alder reactions with the allene moiety to afford fused carbo/heterocycles. Three key intermediates at different stages of the reaction were isolated.
