Citation: SUN Xiang-Ting, ZHANG Dong-Ju, FENG Da-Cheng, LIU Cheng-Bu. Asymmetric Michael Addition between Nitroolefins and Sulfur Ylides Catalyzed by a Thiourea Organocatalyst[J]. Acta Physico-Chimica Sinica, ;2012, 28(03): 561-566. doi: 10.3866/PKU.WHXB201201112 shu

Asymmetric Michael Addition between Nitroolefins and Sulfur Ylides Catalyzed by a Thiourea Organocatalyst

1.
School of Chemistry and Chemical Engineering, Institute of Theoretical Chemistry, Shandong University, Jinan 250100, P. R. China

Received Date: 5 December 2011
Available Online: 11 January 2012
Fund Project: 国家自然科学基金(20873076) (20873076)教育部博士点基金(200804220009)资助项目 (200804220009)

Using density functional theory calculations, we have studied the 1-(2-chlorophenyl)-2-thiourea catalyzed reaction of nitrostyrene with a typical sulfur ylide to understand the Michael addition mechanism. Transition state structures for the C―C bond-forming step controlling the stereoselectivity of the reaction have been identified and their relative stabilities evaluated. The role of the catalyst in the reaction has also been determined. The calculated results show that the formation of the anti-product is energetically more favorable than that of the syn-product. Furthermore, the catalyst (proton donor) promotes the reaction by forming a double hydrogen-bonded complex with nitrostyrene (proton acceptor), where the charge transfer between the donor and acceptor increases the eletrophilicity of β-C atom of the nitrostyrene, favoring the nucleophilic attack of the sulfur ylide.
- Thiourea,
- Nitroolefin,
- Sulfur ylide,
- Asymmetric Michael addition,
- Density functional theory
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