Mechanism of Samarium-Catalyzed 1,5-Regioselective Azide-Alkyne [3+2]-Cycloaddition: A Quantum Mechanical Investigation

被引:14
|
作者
Wang, Jing-Mei [1 ]
Yu, Shang-Bo [2 ]
Li, Zhi-Ming [2 ]
Wang, Quan-Rui [2 ]
Li, Zhan-Ting [2 ]
机构
[1] Fudan Univ, Res Ctr Anal & Measurement, Shanghai 200433, Peoples R China
[2] Fudan Univ, Dept Chem, Shanghai 200433, Peoples R China
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2015年 / 119卷 / 08期
基金
中国国家自然科学基金;
关键词
AB-INITIO; CYCLOADDITION REACTION; CLICK-CHEMISTRY; TRIAZOLE; CONTINUUM; COMPLEXES; LIGATION;
D O I
10.1021/jp5104615
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The mechanism of the samarium-catalyzed 1,5-regioselective azide-alkyne [3 + 2]-cycloaddition (SmAAC) reaction has been examined with quantum mechanical calculations at the B3LYP/6-31+G(d,p) level of theory with ECP51MWB on Sm. Four stepwise pathways were located, with two leading to the 5-endocyclic 1,5-disubstituted 1,2,3-triazole product PSmL2 (paths 1 and 2) and the other two to the exocyclic product ExoPSmCl2 (path 3) as well as 1,4-disubstituted 1,2,3-triazole RegPSmL2 (path 4), respectively. Among them, path 2 (R-COM1-TS12-COM2-TS23-COM3-TS3P-PSmL2) is the most favored one both in the gas phase and in toluene solution, which is in good agreement with the experimental data. Moreover, 1,1-insertion forming COM2 in path 2 is the rate-determining step. The computational results also infer that the participation of samarium catalyst changes the distribution of the electrostatic potential on the reactants' surface, which determines the polarization direction of the reactants and formation of different intermediates (COM1 and RegCOM1), and finally affects the regioselectivity. When solvent corrections for toluene are considered, the 1,1-insertion process is discouraged, while the intramolecular [1,3]-shift reaction is facilitated. © 2015 American Chemical Society.
引用
收藏
页码:1359 / 1368
页数:10
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