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Dynamic kinetic resolution of 2-methyl-2-nitrocyclohexanol: Combining the intramolecular nitroaldol (Henry) reaction & lipase catalysed resolution
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Date
2018-02-02
Authors
Foley, Aoife M.
Gavin, Declan P.
Deasy, Rebecca E.
Milner, Sinéad E.
Moody, Thomas S.
Eccles, Kevin S.
Lawrence, Simon E.
Maguire, Anita R.
Journal Title
Journal ISSN
Volume Title
Publisher
Elsevier B.V.
Published Version
Abstract
Efforts to combine the intramolecular nitroaldol reaction with lipase-catalysed resolution of the resulting nitroaldol adduct in a one-pot dynamic kinetic resolution (DKR) are described. Significant challenges were encountered in the combination of the two systems. trans-2-Methyl-2-nitrocyclohexyl acetate (±)-3b was isolated in excellent enantiopurity (>98% ee) via a sequential DKR sequence where the lipase-mediated resolution and base-mediated interconversion of 2-methyl-2-nitrocyclohexanol 2 were effected alternately, demonstrating the feasibility of this approach initially. Further work showed, for the first time, evidence that a DKR-type system is possible for 2. Reaction engineering allowed the design of a sequential one-pot reaction system which furnished the products with excellent enantioselectivity, and good diastereoselectivity.
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Keywords
Biocatalysis , Kinetic resolution , Henry reaction , Dynamic kinetic resolution , Lipases
Citation
Foley, A. M., Gavin, D. P.; Deasy, R. E., Milner, S. E., Moody, T. S., Eccles, K. S., Lawrence, S. E. and Maguire, A. R. (2018) 'Dynamic kinetic resolution of 2-methyl-2-nitrocyclohexanol: Combining the intramolecular nitroaldol (Henry) reaction & lipase catalysed resolution', Tetrahedron, 74(13), pp. 1435-1443. doi:10.1016/j.tet.2018.01.055