Enantioselective Benzylic Hydroxylation with Pseudomonas monteilii TA‐5: A Simple Method for the Syntheses of (R)‐Benzylic Alcohols Containing Reactive Functional Groups

Abstract

Highly enantioselective benzylic hydroxylations of benzene derivatives (1-4) containing reactive functional groups were achieved for the first time with Pseudomonas monteilii TA-5 as biocatalyst, giving the corresponding (R)-benzylic alcohols 5-8 in 93-99% ee as the only products. Preparative biotransformations were demonstrated by the biohydroxylation of 1 and 2 with resting cells of P. monteilii TA-5 to afford (R)-5 in 94% ee and 66% yield and (R)-6 in 94% ee and 56% yield, respectively. The highly enantioselective biohydroxylations represent a simple access to (R)-benzylic alcohols containing reactive functional groups that are useful pharmaceutical intermediates and versatile chiral building blocks.

Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen

“…141 The enantiocomplementary preparation of ( S )‐ and ( R )‐mandelic acid derivatives by α‐hydroxylation of 2‐arylacetic acids and reduction of α‐ketoester using microbial whole cells ( Helminthosporium ) as well as an enantioselective α‐hydroxylation of 2‐arylacetic acids by an engineered CYP102A1 were reported 142. 143 Enantioselective benzylic hydroxylation using Pseudomonas monteilii allowed a simple approach to the synthesis of ( R )‐benzylic alcohols (Scheme ) 144…”

Biocatalytic asymmetric ring-opening of dihydroisoxazoles: a cyanide-free route to complementary enantiomers of β-hydroxy nitriles from olefins

“…Among them, lipases, 2,22,23 reductases, 1,[24][25][26] dehydrogenases, 27 and nitrilases 28,29 have been mostly employed toward the synthesis of chiral β-hydroxy nitrile via the kinetic resolution of racemic hydroxyl nitriles or the asymmetric reduction of β-oxo-nitriles. In addition, few publications have reported the use of monooxygenase for the asymmetric hydroxylation of 3-phenylpropanenitrile 30 or multi-enzymatic biosynthesis system of alcohol dehydrogenase/halohydrin dehalogenase treating on α-halo ketones and cyanide 31 to form this family of chiral compounds. In part, these biocatalytic methods overcome the use of costly transition-metal catalysts, but are confined to a limited scope of precursors, including keto-nitriles and racemic hydroxyl nitriles, which are prepared using tedious synthetic processes or inevitably use poisonous cyanide as a starting material.…”

Mechanistic Insight into the CO2 Capture by Amidophosphoranes: Interplay of the Ring Strain and the trans Influence Determines the Reactivity of the Frustrated Lewis Pairs

“…To discover more ADHs for the enantioselective oxidation of diols, 8 predicted putative ADH genes from Sphingomonas sp. HXN‐200,15 Pseudomonas medocina TA5,16 and Rhodococcus sp. Moj‐344917 (the genome DNA of these strains were sequenced by our lab) were cloned, expressed, and examined for the oxidations.…”