CuI催化炔基苯甲醛分子内环化反应的理论研究-河北师范大学学报.PDFVIP

35 / 3 / 河北师范大学学报/ / Vol. 35 No. 3 2011 5 JOURNALOFHEBEI NORMAL UNIVERSITY/ Natural Science Edition/ May. 2011 CuI 催化炔基苯甲醛分子内环化反应的理论研究 张金生, 陈 卓, 谢 辉 ( , 550001) : ( DFT) , B3LYP/ 6311G( d, p) CuI . , , . , CuI 163.9 kJ/ mol. CuI * * , Cu , , LP( 2p) C1 C2 C1 C2 O1 . . : DFT ; ; ; ; + : O 641. 12 1 : A : 2011) Theoretical Study on the CuIcatalyzed Intramolecular Cyclization of Alkynylbenzaldehydes ZHANG Jinsheng, CHEN Zhuo, XIE Hui ( School of Chemistry and M aterial Science, Guizhou Normal University,Guizhou Guiyang 550001, China) Abstract:By means of density functional theory ( DFT ) and selfconsistent reaction field of polarizable con tinuum model approach, the onepot synthesis mechanism of cyclic alkenyl ethers via intramolecular cyclization of oalkynylbenzaldehydes catalyzed by CuI has been investigated. The results suggest that the regioselectivity is thermodynamic favoring 6endodig cyclization, and the overall reaction includes the activation of the substrate, an intramolecular cyclization step, a nucleophilic attack of the methanol on the carbonyl carbon, proton migration and the catalyst reproduction. The intramolecular cyclization is the ratecontrolling step in which CuI decreases the relative Gibbs free energy of the transition state by 163. 9kJ/ mol. The catalysis essential of CuI is the coordi * nati