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


Vol. 34,  No. 12, pp. 3591-3596, Dec.  2013
10.5012/bkcs.2013.34.12.3591


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  Abstract

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.

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  Cite this article

[IEEE Style]

N. Lu, H. Wang, Y. Wang, "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, vol. 34, no. 12, pp. 3591-3596, 2013. DOI: 10.5012/bkcs.2013.34.12.3591.

[ACM Style]

Nan Lu, Huatian Wang, and Yangping Wang. 2013. 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, 34, 12, (2013), 3591-3596. DOI: 10.5012/bkcs.2013.34.12.3591.

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ISSN(Print) 0253-2964
ISSN(Online) 1229-5949