69617-84-1Relevant articles and documents
Enzymatic production of both enantiomers of rhododendrol
Musa, Musa M.
, p. 6719 - 6721 (2014)
An asymmetric synthetic approach to produce (R)- and (S)-rhododendrol is described. W110A Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase (W110A Te SADH), an (S)-specific mutant of TeSADH, is used in this approach. The enantioselective redu
Deracemization and Stereoinversion of Alcohols Using Two Mutants of Secondary Alcohol Dehydrogenase from Thermoanaerobacter pseudoethanolicus
Hamdan, Samir M.,Musa, Musa M.,Nafiu, Sodiq A.,Takahashi, Etsuko,Takahashi, Masateru
supporting information, (2020/07/24)
We developed a one-pot sequential two-step deracemization approach to chiral alcohols using two mutants of Thermoanaerobacter pseudoethanolicus secondary alcohol dehydrogenase (TeSADH). This approach relies on consecutive non-stereospecific oxidation of alcohols and stereoselective reduction of their prochiral ketones using two mutants of TeSADH with poor and good stereoselectivities, respectively. More specifically, W110G TeSADH enables a non-stereospecific oxidation of alcohol racemates to their corresponding prochiral ketones, followed by W110V TeSADH-catalyzed stereoselective reduction of the resultant ketone intermediates to enantiopure (S)-configured alcohols in up to > 99 percent enantiomeric excess. A heat treatment after the oxidation step was required to avoid the interference of the marginally stereoselective W110G TeSADH in the reduction step; this heat treatment was eliminated by using sol-gel encapsulated W110G TeSADH in the oxidation step. Moreover, this bi-enzymatic approach was implemented in the stereoinversion of (R)-configured alcohols, and (S)-configured alcohols with up to > 99 percent enantiomeric excess were obtained by this Mitsunobu-like stereoinversion reaction.
Expanding the Substrate Specificity of Thermoanaerobacter pseudoethanolicus Secondary Alcohol Dehydrogenase by a Dual Site Mutation
Musa, Musa M.,Bsharat, Odey,Karume, Ibrahim,Vieille, Claire,Takahashi, Masateru,Hamdan, Samir M.
, p. 798 - 805 (2018/02/21)
Here, we report the asymmetric reduction of selected phenyl-ring-containing ketones by various single- and dual-site mutants of Thermoanaerobacter pseudoethanolicus secondary alcohol dehydrogenase (TeSADH). The further expansion of the size of the substrate binding pocket in the mutant W110A/I86A not only allowed the accommodation of substrates of the single mutants W110A and I86A within the expanded active site but also expanded the substrate range of the enzyme to ketones bearing two sterically demanding groups (bulky–bulky ketones), which are not substrates for the TeSADH single mutants. We also report the regio- and enantioselective reduction of diketones with W110A/I86A TeSADH and single TeSADH mutants. The double mutant exhibited dual stereopreference to generate the Prelog products most of the time and the anti-Prelog products in a few cases.
Selective hydrogenation of conjugated unsaturated ketones containing a hydroxyaryl substituent in the β-position
Kovalenko,Pratsko
, p. 24 - 28 (2017/03/16)
A high selectivity was achieved in the Ni2B-catalyzed hydrogenation of α,β-unsaturated ketones containing a hydroxyaryl (phenolic) substituent in the β-position. The developed hydrogenation procedure was used to synthesize natural compounds of the phenylpropane series and their structural analogs.
Deracemization of Secondary Alcohols by using a Single Alcohol Dehydrogenase
Karume, Ibrahim,Takahashi, Masateru,Hamdan, Samir M.,Musa, Musa M.
, p. 1459 - 1463 (2016/05/02)
We developed a single-enzyme-mediated two-step approach for deracemization of secondary alcohols. A single mutant of Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase enables the nonstereoselective oxidation of racemic alcohols to ketones, followed by a stereoselective reduction process. Varying the amounts of acetone and 2-propanol cosubstrates controls the stereoselectivities of the consecutive oxidation and reduction reactions, respectively. We used one enzyme to accomplish the deracemization of secondary alcohols with up to >99 % ee and >99.5 % recovery in one pot and without the need to isolate the prochiral ketone intermediate.
Synthesis of raspberry and ginger ketones by nickel boride-catalyzed hydrogenation of 4-arylbut-3-en-2-ones
Bandarenko, Mikhail,Kovalenko, Vitaly
, p. 885 - 888 (2014/11/08)
Raspberry and ginger ketones have been synthesized in good yield by the hydrogenation of the corresponding unsaturated precursors 4-(4′- hydroxyphenyl)but-3-en-2-one and 4-(4′-hydroxy-3′-methoxyphenyl)but- 3-en-2-one, respectively, using a freshly prepared suspension of nickel boride in methanol as catalyst.
CYCLIC PEROXIDE OXIDATION OF AROMATIC COMPOUND PRODUCTION AND USE THEREOF
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Page/Page column 10, (2014/10/15)
The present invention provides a method for converting an aromatic hydrocarbon to a phenol by providing an aromatic hydrocarbon comprising one or more aromatic C-H bonds and one or more activated C-H bonds in a solvent; adding a phthaloyl peroxide to the solvent; converting the phthaloyl peroxide to a di-radical; contacting the di-radical with the one or more aromatic C-H bonds; oxidizing selectively one of the one or more aromatic C-H bonds in preference to the one or more activated C-H bonds; adding a hydroxyl group to the one of the one or more aromatic C-H bonds to form one or more phenols; and purifying the one or more phenols.
Transfer hydrogenations of alkenes with formate on Pd/C: Synthesis of dihydrocinchona alkaloids
Wu, Haotian,Hintermann, Lukas
, p. 888 - 892 (2013/05/09)
Protocols for preparative (1-80 gram scale) transfer hydrogenations of alkenes over a palladium on carbon catalyst using formic acid/ammonium formate as hydrogen donor are presented. Cinchona alkaloids have been converted to their dihydro derivatives in >94% yield. Georg Thieme Verlag Stuttgart - New York.
Asymmetric synthesis of enantiomerically pure zingerols by lipase-catalyzed transesterification and efficient synthesis of their analogues
Kitayama, Takashi,Isomori, Sachiko,Nakamura, Kaoru
, p. 621 - 627 (2013/07/19)
The achiral zingerone 1, readily available from ginger, can be easily transformed into chiral derivatives. Zingerol 2, a reduced product of zingerone 1 is expected to be an important new medicinal lead compound. We have achieved a concise synthesis of optically active zingerol (R)-2 and (S)-2 by the lipase-catalyzed stereoselective transesterification of racemic 2. Under the optimized conditions, a lipase from Alcaligenes sp. (Meito QLM) and vinyl acetate in i-Pr2O or hexane at 35 C within 1 h gave the alcohol (S)-2 and the acetate (R)-9 with high enantioselectivity without producing acetylated by-products. Since optically active (S)-2 and (R)-9 were obtained through lipase-catalyzed transesterification, other enantiomerically pure novel compounds could all be synthesized.
Cephalosporolide B serving as a versatile synthetic precursor: Asymmetric biomimetic total syntheses of cephalosporolides C, E, F, G, and (4-OMe-)G
Song, Liyan,Liu, Yuan,Tong, Rongbiao
, p. 5850 - 5853 (2013/12/04)
Cephalosporolide B (Ces-B) was efficiently synthesized and exploited for the first time as a versatile biomimetic synthetic precursor for the chemical syntheses of not only cephalosporolides C, G, and (4-OMe-) G via a challenging diastereoselective oxa-Michael addition but also the structurally unprecedented cephalosporolides E and F via a novel biomimetic ring-contraction rearrangement. These findings provide the first direct chemical evidence that Ces-B may be the true biosynthetic precursor of cephalosporolides.
