beta-nitrostyrene and phosphine

beta-nitrostyrene has been researched along with phosphine* in 1 studies

Other Studies

1 other study(ies) available for beta-nitrostyrene and phosphine

ArticleYear
Sequential catalytic role of bifunctional bicyclic guanidine in asymmetric phospha-Michael reaction.
    Organic & biomolecular chemistry, 2011, Jun-21, Volume: 9, Issue:12

    The catalytic mechanism and origin of enantioselectivity of bicyclic guanidine-catalyzed phospha-Michael reaction between diphenyl phosphine oxide and β-nitrostyrene were investigated by DFT calculations at M06-2X/cc-pVTZ//M06-2X/cc-pVDZ level in conjunction with the implicit SMD solvation method. The catalyst is found to be involved in all 3 steps of the proposed catalytic cycle, namely (1) tautomerization of phosphine oxide, (2) C-P bond formation and (3) concerted hydrogen transfer. The bifunctional role of the guanidine catalyst is clearly demonstrated in all 3 key steps. Due to the geometry of the bicyclic guanidine catalyst, the preferred orientation of the reactants in the transition state of enantioselective C-P bond forming step favours the R enantiomer, in excellent accord with the observed enantioselectivity. Analysis of various transition states suggests that the asymmetric C-P bond formation is controlled by the hydrogen bonding interaction and steric effect between the catalyst and substrate. Various weaker C-H···X (X = N, O and π) interactions also play a role in stabilizing the key transition states.

    Topics: Bridged Bicyclo Compounds; Catalysis; Chemistry, Organic; Crystallography, X-Ray; Guanidine; Hydrogen; Hydrogen Bonding; Models, Molecular; Phenyl Ethers; Phosphines; Quantum Theory; Stereoisomerism; Styrenes

2011