Theoretical Mechanism Studies on the Enantioselectivity of aza-MBH-type Reaction of Nitroalkene to N-tosylimine Catalyzed by Thiourea-tertiary Amine

Bulletin of the Korean chemical society

Huatian Wang¹  Yangping Wang¹  Nan Lu¹ 

关键词: Lewis base;    Weak covalent interaction;    π-π stacking;    Non-covalent interaction;    Density functional theory;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

The enantioselective aza-Morita Baylis Hillman reaction of nitroalkene and N-tosylimine catalyzed by thiourea-tertiary amine has been investigated using density functional theory. Enantioselectivity is dominated by the cooperative effect of non-covalent and weak covalent interactions imposed by different units of catalyst. As Lewis base, the tertiary amine unit activates nitroalkene via weak covalent bond. The weak covalent interaction orients the reaction in a major path with smaller variations of this bond. The aromatic ring unit activates N-tosylimine via π-π stacking. The non-covalent interaction selects the major path with smaller changes of the efficient packing areas. Thiourea unit donates more compact H-bonded network for species of the major path. The calculated ee value in xylene solution phase (97.6%) is much higher than that in N,NDimethylformamide (27.2%). Our conclusion is also supported by NBO analysis.

【 授权许可】

Unknown