36302-36-0

Upstream product

• 24731-17-7 ethyl 2-(2-oxocyclohexyl)acetate 
• 24124-06-9 2-(6-Oxocyclohex-1-enyl) acetate d'ethyle 
• 189636-73-5 3-Oxo-butyric acid (1R,3R)-3-(cyclohex-1-enyloxy)-1-methyl-butyl ester 
• 189636-75-7 Diazo-acetic acid (1R,3R)-3-(cyclohex-1-enyloxy)-1-methyl-butyl ester 
• 189636-77-9 (1R,3R,5R,8S,9S)-3,5-Dimethyl-2,6-dioxa-tricyclo[7.4.0.0^1,8]tridecan-7-one 
• 121898-55-3 (2R,4R)-4-(cyclohex-1-en-1-yloxy)pentan-2-ol 
• 578763-74-3 (1R,6S,7S)-1-((1R,3R)-3-Hydroxy-1-methyl-butoxy)-bicyclo[4.1.0]heptane-7-carboxylic acid ethyl ester 

Downstream Products

• 884048-54-8 trans-2-Carboxymethylcyclohexanol 
• 74708-16-0 (3aS,7aS)-hexahydrobenzofuran-2(3H)-one 
• 204447-96-1 ((1S,2R)-2-Hydroxy-cyclohexyl)-acetic acid ethyl ester 
• 204448-00-0 ((1S,2S)-2-Hydroxy-cyclohexyl)-acetic acid ethyl ester 

Relevant academic research and scientific papers

Biocatalytic access to nonracemic γ-oxo esters: Via stereoselective reduction using ene-reductases

The asymmetric bioreduction of α,β-unsaturated γ-keto esters using ene-reductases from the Old Yellow Enzyme family proceeds with excellent stereoselectivity and high conversion levels, covering a broad range of acyclic and cyclic derivatives. Various strategies were employed to provide access to both enantiomers, which are versatile precursors of bioactive molecules. The regioselectivity of hydride addition on di-activated alkenes was elucidated by isotopic labeling experiments and showed strong preference for the keto moiety as activating/binding group as opposed to the ester. Finally, chemoenzymatic synthesis of (R)-2-(2-oxocyclohexyl)acetic acid was achieved in high ee on a preparative scale combining enzymatic reduction followed by ester hydrogenolysis.

Chiral and flexible 2,4-pentanediol-tethered cyclopropanation of olefins with a carbenoid derived from a diazo ester to construct three stereogenic centers

2,4-Pentanediol-tethered cyclopropanation of an olefin with an internal carbenoid generated from a diazo ester proceeded smoothly to give a chiral adduct having three stereogenic centers under full stereocontrol. The high stereoselectivity was not affected by the structure of the olefinic portion, studied so far with six substrates. Conversion of the product cyclopropane to other optically active compounds is also reported.

Synthesis of natural product precursors by Baeyer-Villiger oxidation with cyclohexanone monooxygenase from Acinetobacter

The Baeyer-Villiger oxidation of the 2-substituted ketones 1 and 3 with the coupled system cyclohexanone monooxygenase from Acinetobacter NCIMB 9871/formate dehydrogenase from Pseudomonas sp. 101 provides the lactones (R)-2 and (R)-4 with high enantiomeric excess which are precursors in the synthesis of lipoic acid. The symmetrically trisubstituted ketone 5 was oxidised to the lactones 6a and 6b in a ratio of approx. 3:1. The absolute configuration of 6a and 6b was determined by hydrolysis of the racemic lactone with PLE yielding the hydroxycarboxylic acid (-)-7 with known absolute configuration.

Application of Enzymic Baeyer-Villiger Oxidations of 2-Substituted Cycloalkanones to the Total Synthesis of (R)-(+)-Lipoic Acid

Oxidation of ketones 1a-h using a monooxygenase from Pseudomonas putida NCIMB 10007 gave the lactones 2a-h in optically active form: lactone 2h was converted into (R)-(+)-lipoic acid 9.