铂催化2-烯炔苯甲醛水合环化反应的机理及化学选择性的理论研究

doi:10.7503/cjcu20150649

摘要/Abstract

摘要：

采用密度泛函理论(DFT)的计算方法, 研究了铂催化2-烯炔基苯甲醛水合环化反应的微观机理及化学选择性的根源. 计算结果表明, 首先炔基被催化活化而发生亲核环化生成吡喃铂中间体; 接着吡喃铂中间体与烯烃双键发生[3+2]环加成生成铂-碳卡宾复合物; 之后, 反应将沿2条路径进行, 得到产物3a或4a, 其中4a的生成需经两步水分子辅助的质子转移过程. 生成产物3a需要克服的活化能垒为146.5 kJ/mol; 对4a的生成, 烯醇式和酮式互变异构是决速步聚, 当一个水分子参与反应时, 对应的能垒为185.8 kJ/mol, 当2个和3个水分子参与反应时, 能垒分别降低到128.1和64.9 kJ/mol. 因此, 水分子参与催化得到产物4a的路径是有利的. 另外, 反应的选择性与在异构化过程中水的共催化作用有关. 以上结果很好地解释了实验现象, 并为铂催化水环化反应提供新的见解.

关键词: 铂催化, 化学选择性, 水合环化反应, 反应机理, 密度泛函理论

Abstract:

With the aid of density functional theory(DFT) calculations, we made a detailed mechanism study on the origin of chemoselectivity in Pt-catalyzed hydrative cyclizations of 2-enynylbenzaldehydes. The calculations indicate that the formation of platinum-pyrylium intermediate is initiated by the activation of alkyne. Successive [3+2] cycloaddition with a double bond leads to the platinum-carbene complex. After that, the reaction proceeds along either pathway Ⅰ or pathway Ⅱ to yield products 3a and 4a, depending on the subsequent two-step water-assisted proton-transfer process. The calculated barrier leading to product 3a is 146.5 kJ/mol. For the formation of product 4a, the tautomerization(from enol to keto form) is the rate-determining step with a barrier of 185.8 kJ/mol when one water molecule is involved. However, when two and three water molecules are involved in catalysis, the barrier is reduced to 128.1 and 64.9 kJ/mol respectively. Therefore, the reaction preferentially proceeds along the pathway Ⅱ leading to product 4a. Water molecules that act as a cocatalyst in the tautomerization process are mainly responsible for the good selectivity. This result rationalizes well the experimental observations and provides a new insight into the Pt-catalyzed hydrative cyclizations.

Key words: PtCl2 catalysis, Chemoselectivity, Hydrative cyclization, Mechanism, Density functional thoery

中图分类号:

O641

TrendMD:

郭今心, 朱荣秀, 张冬菊, 李明霞, 刘成卜. 铂催化2-烯炔苯甲醛水合环化反应的机理及化学选择性的理论研究. 高等学校化学学报, 2015, 36(11): 2262.

GUO Jinxin, ZHU Rongxiu, ZHANG Dongju, LI Mingxia, LIU Chengbu. Theoretical Studies on the Mechanism of Water-dependent Chemoselectivity in the Pt-Catalyzed Hydrative Cyclization of 2-Enynylbenzaldehydes. Chem. J. Chinese Universities, 2015, 36(11): 2262.

图/表 8

Scheme 1 PtCl2-catalyzed hydrative cyclization of 2-enynylbenzaldhydes reported by Chang et al.[1]

Scheme 2 Proposed mechanism for formation of 4a reported by Chang et al.[1]

Scheme 3 Schematic geometries for the formation of platinium-carbene complex IM3 The values in parentheses are calculated relative free energies(kJ/mol) in toluene solution.

Fig.1 Calculated free energy(kJ/mol) profile in toluene solution for the formation of 3a-PtCl2 along pathway I

Fig.2 Geometric structures for intermediates and transition states in pathway Ⅰ(formation of 3a) Bond lengths are in nm.

Fig.3 Calculated free energy(kJ/mol) profile in toluene solution for the formation of 4a-PtCl2 along pathway II

Fig.4 Geometric structures for intermediates and transition states in pathway Ⅱ(formation of 4a) Bond lengths are in nm.

Table 1 Calculated partial natural bond orbital(NBO) charges on three structures TS44a, TS4'4a and TS4″4a

Structure	NBO charge/e
Structure	C1	C2	O1	H	Pt	O2
TS4^4a	0.44	-0.27	-0.77	0.51	0.63	-0.90
TS4'^a	0.49	-0.32	-0.75	0.49	0.62	-0.92
TS4″^4a	0.57	-0.37	-0.70	0.44	0.64	-0.93

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