The immobilisation of chiral organocatalysts on magnetic nanoparticles: the support particle cannot always be considered inert.
Citation:Gleeson O, Davies GL, Peschiulli A, Tekoriute R, Gun'ko YK, Connon SJ, The immobilisation of chiral organocatalysts on magnetic nanoparticles: the support particle cannot always be considered inert., Organic & biomolecular chemistry, 9, 22, 2011, 7929-40
c1ob06110k.pdf (Published (publisher's copy) - Peer Reviewed) 776.0Kb
A systematic study concerning the immobilisation onto magnetic nanoparticles of three useful classes of chiral organocatalyst which rely on a confluence of weak, easily perturbed van der Waals and hydrogen bonding interactions to promote enantioselective reactions has been undertaken for the first time. The catalysts were evaluated in three different synthetically useful reaction classes: the kinetic resolution of sec-alcohols, the conjugate addition of dimethyl malonate to a nitroolefin and the desymmetrisation of meso anhydrides. A chiral bifunctional 4-N,N-dialkylaminopyridine derivative could be readily immobilised; the resulting heterogeneous catalyst is highly active and is capable of promoting the kinetic resolution of sec-alcohols with synthetically useful selectivity under process-scale friendly conditions and has been demonstrated to be reusable in a minimum of 32 consecutive cycles. The immobilisation of a cinchona alkaloid-derived urea-substituted catalyst proved considerably less successful in terms of both catalyst stability and product levels of enantiomeric excess. An immobilised cinchona alkaloid-derived sulfonamide catalyst was also prepared, with mixed results: the catalyst exhibits outstanding recyclability on a par with that associated with the successful N,N-dialkylaminopyridine analogue, however product enantiomeric excess is consistently lower than that obtained using the corresponding homogeneous catalyst. While no physical deterioration of the heterogeneous catalysts was detected on analysis after multiple recycles, in the cases of both the conjugate addition to nitroolefins and the desymmetrisation of meso anhydrides, significant levels of background catalysis by the nanoparticles in the absence of the organocatalyst was detected, which explains in part the poor performance of the immobilised organocatalysts in these reactions from a stereoselectivity standpoint. It seems clear that the immobilisation of sensitive chiral organocatalysts onto magnetite nanoparticles does not always result in heterogeneous catalysts with acceptable activity and selectivity profiles, and that consequently the applicability of the strategy must be ascertained (until more data is available) on a case-by-case basis
Type of material:Journal Article
Series/Report no:Organic & biomolecular chemistry
Availability:Full text available
Keywords:Bifunctional; Catalyst stability; Conjugate addition; Dimethyl malonate; Enantiomeric excess; Enantioselective reactions; Heterogeneous catalyst; Homogeneous catalyst; Hydrogen bonding interactions; Immobilisation; Kinetic resolution; Magnetic nanoparticles; Magnetite nanoparticles; Nitroolefins; Organocatalysts; Poor performance; Recyclability; Sec-alcohols; Systematic study; Van der waals