Constraining Asymmetric Organometallic Catalysts within Mesoporous Supports Boosts Their Enantioselectivity

By constraining tethered asymmetric organometallic catalysts within the nanopores of silica supports so as to increase the interaction between the pore wall and the active center (and hence to restrict access of the reactant to the catalyst), a significant improvement in enantioselectivity is achiev...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2003-12, Vol.125 (49), p.14982-14983
Main Authors: Raja, Robert, Thomas, John Meurig, Jones, Matthew D, Johnson, Brian F. G, Vaughan, David E. W
Format: Article
Language:English
Subjects:
Chemical reactivity
Chemistry
Exact sciences and technology
Organic chemistry
Reactivity and mechanisms
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Summary:By constraining tethered asymmetric organometallic catalysts within the nanopores of silica supports so as to increase the interaction between the pore wall and the active center (and hence to restrict access of the reactant to the catalyst), a significant improvement in enantioselectivity is achieved. A schematic illustration of a cationic chiral, organometallic catalyst, [Rh(I)(COD)PMP] {(S)-(+)-1-(2-pyrrolidinylmethyl)-pyrrolidine and cyclooctadiene}, which is noncovalently anchored via a N−H···F hydrogen bond with the triflate ion, CF3SO3 -, to the curved inner surface of a 38 Å diameter pore of a silica support for the asymmetric hydrogenation of the CO bond in methyl benzoylformate to the corresponding methyl mandelate is shown. Rh (purple); N (blue); H (white); F (green); C (gray); S (yellow); O (red).
ISSN:0002-7863
1520-5126
DOI:10.1021/ja030381r