919113-09-0Relevant articles and documents
Bifunctional Iminophosphorane Catalyzed Enantioselective Sulfa-Michael Addition to Unactivated α-Substituted Acrylate Esters
Farley, Alistair J. M.,Sandford, Christopher,Dixon, Darren J.
supporting information, p. 15992 - 15995 (2016/01/15)
The highly enantioselective sulfa-Michael addition of alkyl thiols to unactivated α-substituted acrylate esters catalyzed by a bifunctional iminophosphorane organocatalyst under mild conditions is described. The strong Br?nsted basicity of the iminophosphorane moiety of the catalyst provides the necessary activation of the alkyl thiol pro-nucleophile, while the two tert-leucine residues flanking a central thiourea hydrogen-bond donor facilitate high enantiofacial selectivity in the protonation of the transient enolate intermediate. The reaction is broad in scope with respect to the alkyl thiol, the ester moiety, and the α-substituent of the α,β-unsaturated ester, affords sulfa-Michael adducts in excellent yields (up to >99%) and enantioselectivities (up to 96% ee), and is amenable to decagram scale-up using catalyst loadings as low as 0.05 mol %.
Stereoselective nucleophilic addition to imines catalyzed by chiral bifunctional thiourea organocatalysts
Puglisi, Alessandra,Benaglia, Maurizio,Annunziata, Rita,Rossi, Davide
experimental part, p. 2258 - 2264 (2009/04/04)
A new and easy synthesis of chiral bifunctional organic catalysts obtained by the combination of (S)-t-leucine-derivatives with (1R,2R)-trans-1,2-diamino-cyclohexane was developed. A few compounds, representatives of a class of organocatalysts containing a thiourea group and a tertiary amino group connected through a chiral backbone, have been successfully synthesized. The catalytic behaviour of such bifunctional chiral molecules, either neutral or protonated species, was investigated in the addition of acetylacetone to β-nitrostyrene as a model reaction. Using the best conditions, high yields and enantioselectivities of up to 85% were obtained. The same metal free catalysts were then employed in the addition of activated nucleophiles to imines: in the reaction of 1,3-diketones with N-CBz imines, the products were isolated in up to 61% ee, while in the reaction with diethyl malonate enantioselectivities up to 71% were reached.
Highly enantioselective aza-Baylis-Hillman reactions catalyzed by chiral thiourea derivatives
Raheem, Izzat T.,Jacobsen, Eric N.
, p. 1701 - 1708 (2007/10/03)
We report the discovery of asymmetric aza-Baylis-Hillman (ABH) reactions of N-p-nitrobenzenesulfonylimines with methyl acrylate catalyzed by chiral thiourea derivatives. A series of aromatic imines was found to undergo coupling with methyl acrylate with u
