Record 11660   View: Standard Glossary  HistCite Guide
Author(s): Shi FQ; Song BA
Title: Origins of enantioselectivity in the chiral Bronsted acid catalyzed hydrophosphonylation of imines
Source: ORGANIC & BIOMOLECULAR CHEMISTRY 7 (7): 1292-1298
Date: 2009 
Document Type: Journal : Review
DOI:  
Language: English
Comment:  
Address: Guizhou Univ, Ctr Res & Dev Fine Chem, Minist Educ, Key Lab Green Pesticide & Agr Bioengn, Guiyang 550025, Peoples R China.
Reprint: Shi, FQ, Guizhou Univ, Ctr Res & Dev Fine Chem, Minist Educ, Key Lab
Green Pesticide & Agr Bioengn, Guiyang 550025, Peoples R China.
E-mail: fcc.fqshi@gzu.edu.cn
Author Keywords:  
KeyWords Plus: ALPHA-AMINO PHOSPHONATES; FRIEDEL-CRAFTS REACTION; PHASE-TRANSFER CATALYSIS; MANNICH-TYPE REACTION; DIELS-ALDER REACTION; POLARIZABLE CONTINUUM MODEL; BAYLIS-HILLMAN REACTION; ASYMMETRIC-SYNTHESIS; PHOSPHORIC-ACID; TRANSFER HYDROGENATION
Abstract: The results of an experimental and ONIOM-based computational investigation of the mechanism and the origins of enantioselectivity in the asymmetric synthesis of alpha-amino phosphonates by an enantioselective hydrophosphonylation of imines catalyzed by chiral Bronsted acids are reported. It was found that the enantioselectivity observed in the enantioselective hydrophosphonylation of the imine with a benzothiazole moiety was poor. A detailed computational study with a two-layer ONIOM (B3LYP/6-31G(d)/AM1) method on the mechanism of the investigated reaction was carried out to explore the origins of the enantioselectivity. Calculations indicate that the investigated reaction is a two-step process involving proton-transfer and nucleophilic addition, which is the stereo-controlling step. The investigated reaction prefers a di-coordination pathway to a mono-coordination pathway. The different enantioselectivities exhibited by three kinds of catalyst and two kinds of nucleophile were rationalized. Calculations indicate that si-facial attack is higher in energy than re-facial attack by only 0.1 kcal/mol, which accounts well for the low ee value observed in the enantioselective hydrophosphonylation of the imine with a benzothiazole moiety. The energy barrier for phosphonate-phosphite tautomerism catalyzed by chiral Bronsted acid in toluene is only 1.8 kcal/mol, which could explain why the investigated reaction can take place at room temperature.
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