Facile one-pot synthesis of a novel all-carbon stair containing dimerized pentalene core from alkyne  

作　　者：Hui Zhao Rakesh Kumar Gupta Wei Zhang Jiong Jia Qun Yu Zhiyong Gao Guilin Zhuang Dacheng Li Xingpo Wang Chen Ho Tung Di Sun 

机构地区：[1]Key Laboratory of Colloid and Interface Chemistry,Ministry of Education,School of Chemistry and Chemical Engineering,State Key Laboratory of Crystal Materials,Shandong University,Ji’nan 250100,China [2]College of Chemical Engineering and Materials Science,Zhejiang University of Technology,Hangzhou 310032,China [3]School of Chemistry and Chemical Engineering,Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals,Key Laboratory of Green Chemical Media and Reactions,Ministry of Education,Henan Normal University,Xinxiang 453007,China [4]Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology,and School of Chemistry and Chemical Engineering,Liaocheng University,Liaocheng 252000,China

出　　处：《Chinese Chemical Letters》2022年第4期2047-2051,共5页中国化学快报（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (Nos. 91961105, 21822107,21571115, 21827801);the Natural Science Foundation of Shandong Province (Nos. ZR2019ZD45, JQ201803 and ZR2017MB061);the Taishan Scholar Project of Shandong Province of China (Nos.tsqn201812003 and ts20190908);Project for Scientific Research Innovation Team of Young Scholar in Colleges and Universities of Shandong Province (No. 2019KJC028);Natural Science Foundation of Shandong Province (No. ZR2020ZD35)。

摘　　要：The construction of all-carbon molecule frameworks remains challenging. Herein, we report a facile and efficient one-pot synthesis of a novel all-carbon stair containing dimerized pentalene core using inexpensive cyclopropyl alkyne catalyzed by in situ generated Cu(I) from the comproportionation reaction of Cu(II) salt and Cu powder under mild reaction conditions. The reaction proceeds via sequential acetylenic coupling, followed by cyclization and [2 + 2] cycloaddition to directly produce pentalene dimer, which is difficult to access by other established methods. Different mechanistic paths were studied for the pentalene formation using density functional theory, suggesting that the reaction also proceeds through acetylenic coupling followed by cyclization and [2 + 2] cycloaddition. Based on the activation energy barriers, Path 1 has the rate-determining step of 38.63 kcal/mol, which is the most thermodynamically preferred one among the four paths.

关 键 词：One-pot synthesis Penatlene dimerization Comproportionation reaction Crystal structure Theoretical calculations 

分 类 号：TQ317[化学工程—高聚物工业]