Pd‐catalyzed bicyclization of 2‐alkynylhalobenzenes and propargylic alcohols for the formation of indeno[1,2]furans: a DFT study
Pd‐catalyzed bicyclization of 2‐alkynylhalobenzenes and propargylic alcohols for the formation of indeno[1,2]furans: a DFT study
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DOI：
10.1002/poc.3271
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发表时间：
2014-03
影响因子：
1.8
通讯作者：
Liu Yang;Gerui Ren;Xincheng Ye;Xianyong Que;Qun-fang Lei;Wenjun Fang;Hujun Xie
中科院分区：
文献类型：
--
作者：
Liu Yang;Gerui Ren;Xincheng Ye;Xianyong Que;Qun-fang Lei;Wenjun Fang;Hujun Xie
用密度泛函理论（DFT）研究了钯催化的2-炔卤代苯与炔丙醇双环反应生成茚并[1，2]呋喃的机理.针对不同反应底物之间的不同反应方程计算了全自由能分布。计算结果表明，该催化循环包括氧化加成、配体取代、第一次C → C三键插入、重排、第二次C → C三键插入和还原消除6个步骤，其中还原消除是不同反应式（1）、（2）和（3）的速率控制步骤.我们的计算结果与实验观测结果是一致的。版权所有© 2014约翰威利父子有限公司.
The mechanism of palladium-catalyzed bicyclization of 2-alkynylhalobenzenes and propargylic alcohols for the formation of indeno[1,2]furans has been studied computationally with the aid of density functional theory (DFT). Full free energy profiles are computed for different reaction equations between different reaction substrates. The calculation results showed that the catalytic cycle is found to contain six steps, oxidative addition, ligand substitution, first C ≡ C triple bond insertion, rearrangement, second C ≡ C triple bond insertion and reductive elimination, with the reductive elimination being the rate-determining step for the different reaction equations (1), (2) and (3). Our calculations are consistent with experimental observations. Copyright © 2014 John Wiley & Sons, Ltd.