13672-64-5Relevant articles and documents
Biocatalytic access to nonracemic γ-oxo esters: Via stereoselective reduction using ene-reductases
Turrini, Nikolaus G.,Cioc, Rǎzvan C.,Van Der Niet, Daan J. H.,Ruijter, Eelco,Orru, Romano V. A.,Hall, Mélanie,Faber, Kurt
, p. 511 - 518 (2017/08/14)
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.
Thiol-catalyzed acyl radical cyclization of alkenals
Yoshikai, Kazuya,Hayama, Tomoharu,Nishimura, Katsumi,Yamada, Ken-Ichi,Tomioka, Kiyoshi
, p. 681 - 683 (2007/10/03)
(Chemical Equation Presented) Thiol-catalyzed direct generation of acyl radicals and their intramolecular addition to olefins of alkenals gave 2-substituted five- and six-membered cyclic ketones in reasonably good yields. The combination of odorless tert-dodecanthiol and AIBN or V-40 was the initiator of choice among surveyed radical generators for the cyclization of alkenals. Aldehydes having electron-deficient olefins cyclized more easily than those having unactivated olefins.
Stereoselectivity in hydrosilylative reduction of substituted cyclohexanone derivatives with chiral rhodium-bis(oxazolinyl)pyridine catalyst
Nishiyama,Park,Itoh
, p. 1029 - 1034 (2007/10/02)
Stereoselectivity in the reduction of substituted cyclohexanones, 4-tert-butylcyclohexanone, 2-methylcyclohexanone, 2-phenylcyclohexanone, and 2-methoxycarbonyl-methylcyclohexanone, was examined with chiral rhodium-bis(oxazolinyl)pyridine catalyst and diphenylsilane. 4-tert-Butylcyclohexanone gave the corresponding trans(equatorial)-alcohol predominantly; the ratio of the trans/cis alcohols, 67:33. Other 2-substituted cyclohexanones showed exclusive enantioselectivities for each diastereomer in terms of the kinetic resolution; e.g. from 2-phenylcyclohexanone, 99% ee of (1S,2R)-trans-2-phenylcyclohexanol and 96% ee of (1S,2S)-cis-2-phenylcyclohexanol in 92% yield (the trans/cis ratio = 51:49).