Citation: ZHAO Yi, ZHOU Jin, LIU Hui, ZHUO Shu-Ping. Reaction Mechanism and the Regioselectivity of Cu-Catalyzed Silacarboxylation of Internal Alkynes: a Density Functional Theory Study[J]. Acta Physico-Chimica Sinica, ;2015, 31(10): 1864-1871. doi: 10.3866/PKU.WHXB201508281 shu

Reaction Mechanism and the Regioselectivity of Cu-Catalyzed Silacarboxylation of Internal Alkynes: a Density Functional Theory Study

1.
School of Chemical Engineering, Shandong University of Technology, Zibo 255049, Shandong Province, P. R. China

Received Date: 1 July 2015
Available Online: 28 August 2015
Fund Project: 国家自然科学基金(51302156, 21302057) (51302156, 21302057)山东省自然科学基金联合专项(ZR2014BL012)资助项目 (ZR2014BL012)

Transition metal-catalyzed carbon-carbon bond formation utilizing CO₂ is of great importance. The heteroatom functionality and CO₂ are simultaneously and catalytically incorporated into unsaturated substrates to form highly functionalized carboxylic acid derivatives. Here, density functional theory (DFT) is used to study the reaction mechanisms of the Cu-catalyzed silacarboxylation of internal alkynes. Two possible paths were proposed depending on the relative positions of the substituents (path I: methyl and path II: phenyl). The calculations reveal that the initial alkyne insertion into the Cu―Si bond determined both the rate and the selectivity. In path I, the calculated free energy barrier for alkyne insertion is 112.8 kJ·mol^-1, while that in path II is 127.6 kJ·mol^-1. Thus, path I is more kinetically favorable than path II, which is consistent with the experimentally observed product ratio of 97 : 3. Our analysis revealed that the electronic effects of the alkyne substituents dominated the observed regioselectivity.
- Regioselectivity,
- Alkyne,
- Silacarboxylation,
- Carbon dioxide,
- Density functional theory
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