278600-41-2Relevant academic research and scientific papers
Theoretical prediction of selectivity in kinetic resolution of secondary alcohols catalyzed by chiral DMAP derivatives
Larionov, Evgeny,Mahesh, Mohan,Spivey, Alan C.,Wei, Yin,Zipse, Hendrik
supporting information; scheme or table, p. 9390 - 9399 (2012/07/14)
The mechanism of esterification of the secondary alcohol 1-(1-naphthyl)ethanol 9 by isobutyric anhydride catalyzed by 4-pyrrolidinopyridine (PPY, 11) and a series of single enantiomer atropisomeric 4-dialkylaminopyridines 8a-g has been studied computationally at the B3LYP/6-311+G(d,p)//B3LYP/6-31G(d) level. Comparison of the levels of enantioselectivity predicted computationally with the results obtained experimentally allowed the method to be validated. The value of the approach is demonstrated by the successful prediction that a structural modification of an aryl group within the catalyst from phenyl to 3,5-dimethylphenyl would lead to improved levels of selectivity in this type of kinetic resolution (KR) reaction, as was subsequently verified following synthesis and evaluation of this catalyst (8d). Experimentally, the selectivity of this type of KR is found to exhibit a significant deuterium isotope effect (for 9 vs d1-9).
Chiral catalysts for asymmetric acylation and related transformations
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, (2008/06/13)
A chiral catalyst comprising a 3,4-disubstituted pyridine, or a salt, N functionalized derivative, dimer or oligomer thereof, wherein the 3-substituent is substantially hindered from rotation about the bond (sp2-sp2 biaryl axis) link
Axially chiral analogues of 4-(dimethylamino)pyridine: Novel catalysts for nonenzymatic enantioselective acylations
Spivey, Alan C.,Fekner, Tomasz,Spey, Sharon E.
, p. 3154 - 3159 (2007/10/03)
A concise seven-step synthesis of atropisomeric 3-aryl analogues of DMAP from 4-pyridone 8 has been developed. A representative compound of this class, biaryl (±)-15, has been resolved using CSP HPLC and shown to be an efficient nucleophilic catalyst for kinetic resolution of a series of secondary alcohols on both an analytical and preparative scale (stereoselectivity factors, s = 8.9-29).
