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. 2018 May 25;7(5):393-400.
doi: 10.1002/open.201800056. eCollection 2018 May.

Cascade Reaction by Chemo- and Biocatalytic Approaches to Obtain Chiral Hydroxy Ketones and anti 1,3-Diols

Raffaella Gandolfi  1 , Giorgio Facchetti  1 , Michael S Christodoulou  1 , Marco Fusè  2 , Fiorella Meneghetti  1 , Isabella Rimoldi  1
Affiliations

Cascade Reaction by Chemo- and Biocatalytic Approaches to Obtain Chiral Hydroxy Ketones and anti 1,3-Diols

Raffaella Gandolfi et al. ChemistryOpen. .

Abstract

A chemo- and biocatalytic cascade approach was applied for the stereoselective synthesis of hydroxy ketones and the corresponding 1,3-diols. A new class of tridentate N,N,O ligands was used with copper(II) complexes for the asymmetric β-borylation of α,β-unsaturated compounds. The complex containing ligand L5 emerged as the best performer, and it gave the organoborane derivatives with good ee values. The corresponding keto-alcohol compounds were then bioreduced by yeasts. The biotransformation set up with Rhodotorula rubra allowed (R)-keto-alcohols and (S,S)-diols to be obtained with up to 99 % ee and up to 99 % de in favor of the anti enantiomers.

Keywords: biocatalysis; borylation; copper; reduction; yeast.

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Figures

Scheme 1
Scheme 1
Combining transition‐metal catalysis with a biocatalytic approach to obtain diols.
Scheme 2
Scheme 2
Synthesis of ligands. Reagents and conditions: i) EtOH, RT, 5 h; ii) NaBH4, THF/CH2Cl2, 0 °C, 1 h.
Figure 1
Figure 1
ORTEP9 view of the asymmetric unit with an arbitrary atom‐numbering scheme (ellipsoids are drawn at 40 % probability). H atoms are shown as spheres of arbitrary radii.
Scheme 3
Scheme 3
Proposed reaction mechanism.
See this image and copyright information in PMC

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