Diastereoselective Oxidation Research Articles

Diastereoselective oxidation of sulfides to sulfoxides. Synthesis of novel C-6 sulfoxy tetrahydromevinic acids

The synthesis and diastereoselective oxidation of novel tetrahydromevinic acid lactone sulfides to sulfoxides is described.

Enantio- and diastereoselective transformations of cycloheptatriene to sugars and related products

Both meso diastereomers of 6-[tert-butyldimethylsilyl)oxy]-2-cycloheptene-1,4-diol, prepared from cycloheptatriene, have been enzymatically asymmetrized by conversion to monoacetates using Pseudomonas cepacia lipase in isopropenyl acetate. A study of protecting group manipulations, diastereoselective oxidations, and regioselective ring openings utilizing these enantiopure monacetates which results in the synthesis of all possible methyl 2,4-dideoxyhexopyranosides is described

Chiral Sulfinylethenes as Efficient Dienophiles for Asymmetric Diels-Alder Reactions

Abstract An overview of our recent studies on asymmetric Diels-Alder reactions of chiral vinyl sulfoxides (= sulfinylethenes) is described. For the preparation of sulfinylethenes as Diels-Alder dienophiles, the Andersen method as well as a novel route by diastereoselective oxidation of exo-2-hydroxy-10-bornyl vinyl sulfides with 3-chloroperoxybenzoic acid (m-CPBA) is presented. The latter methodology has been successfully applied to a facile synthesis of two types of novel sulfoxides, i.e., α-sulfinylmaleate and α-sulfinylmaleimide derivatives. These sulfinyl dienophiles effect Diels-Alder reactions with a high degree of diastereoselectivity. Especially, the chiral α-sulfinylmaleimides readily react with Diels-Alder dienes of rather low reactivity, such as furan, to give the corresponding cycloadducts under conventional conditions. Applications of these asymmetric Diels-Alder reactions to natural product synthesis are also described.

Synthesis and asymmetric Diels–Alder reaction of dimethyl (‘d-isoborneol-10-sulphinyl’)maleate: novel route to key intermediates for synthesis of some carbocyclic nucleosides and terpenoids

The chiral sulphoxide 1 was synthesized from 10-mercaptoisoborneol via diastereoselective oxidation. The dienophile 1 reacted with cyclopentadiene in the presence of a Lewis acid to give the adducts 7 and 8 with high diastereoselectivity (∼100%). Diels–Alder reaction of 1 in the absence of a Lewis acid afforded the adduct 9 as the major product with reversed diastereoselectivity. The adduct 7 was transformed into a useful precursor 11 for synthesis of carbocyclic nucleosides. The adducts 7 and 9 were converted into a bridged bicyclic lactone 21 in an enantiodivergent manner via selective reduction followed by reaction with samarium diiodide.

ChemInform Abstract: Asymmetric Reactions of Sulfoxides Derived from Diastereoselective Oxidation of 2‐Alkylthio‐2′‐hydroxy‐1,1′‐binaphthalenes.

AbstractThermolysis of the binaphthyl bis(dimethylthiocarbamate) (I) yields the mixed ester (II) which is converted into the thioethers (V) upon hydrolysis and reaction with the alkyl halides (IV).

Asymmetric Reactions of Sulfoxides Derived from Diastereoselective Oxidation of 2-Alkylthio-2′-hydroxy-1,1′-binaphthalenes

Asymmetric Reactions of Sulfoxides Derived from Diastereoselective Oxidation of 2-Alkylthio-2′-hydroxy-1,1′-binaphthalenes

Diastereoselective oxidation of sulfides to sulfoxides with potassium peroxymonosulfate

Potassium peroxymonosulfate oxidation of sulfides to sulfoxides occurs with high diastereoselectivity.

Silicon‐Directed Regio‐ and Enantioselective Synthesis of α‐Hydroxy‐ketones Preliminary Communication

Abstractα‐Silylated ketones (S)−2 (ee ≥ 98%), easily available through silylation or silylation/alkylation from ketones 1 using the (−)‐(S)‐1‐amino‐2‐(methoxymethyl)pyrrolidine (SAMP)−/(+)‐(R)‐1‐amino‐2‐(methoxymethyl)pyrrolidine (RAMP)‐hydrazone method, are oxidized to give α‐hydroxy‐ketones (R)−5 of high enantiomeric purity (ee ≥ 98%) and in good overall yields (51‐70%). The key step of the procedure is the silicon‐directed diastereoselective oxidation of the corresponding silyl enol ethers of (S)−2, with m‐chloroperbenzoic acid or 3‐phenyl‐2‐(phenylsulfonyl)oxaziridine, followed by flash chromatography and desilylation.

Reactions of an allylic sulfide, sulfoxide, and sulfone with singlet oxygen. The observation of a remarkable diastereoselective oxidation

Oxydation de sulfone-, sulfoxyde- et sulfure de [dimethyl-2',3' butene-2']yle et de p-tolyle

Self-induced diastereoselective oxidation of vinyl sulfoxides bearing a chiral hydroxy group as a way of preparation of optically active sulfinyl dienophiles and their use in the asymmetric Diels-Alder reactions to cyclopentadiene [Erratum to document cited in CA104(21):186036k

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSelf-induced diastereoselective oxidation of vinyl sulfoxides bearing a chiral hydroxy group as a way of preparation of optically active sulfinyl dienophiles and their use in the asymmetric Diels-Alder reactions to cyclopentadiene [Erratum to document cited in CA104(21):186036k]Ottorino De Lucchi, Vittorio Lucchini, Carla Marchioro, Giovanni Valle, and Giorgio ModenaCite this: J. Org. Chem. 1989, 54, 13, 3245Publication Date (Print):June 1, 1989Publication History Published online1 May 2002Published inissue 1 June 1989https://doi.org/10.1021/jo00274a065RIGHTS & PERMISSIONSArticle Views42Altmetric-Citations7LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (73 KB) Get e-Alerts Get e-Alerts

Microbiologically Catalyzed Enantio- and Diastereoselective Oxidation of Chrysanthemol Stereoisomers to Chrysanthemic Acids

The diastereo- and enantioselective microbial oxidation of a mixture of racemic cis/trans-chrysanthemols to the corresponding stereoisomeric chrysanthemic acids by Aspergillus species is described. Of the three microorganisms which were found capable of oxidizing racemic cis/trans-chrysanthemols, A. ochraceus ATCC 18500 showed complete enantioselectivity for (+)-stereoisomers [(+)-trans-chrysanthemol and (+)-cis-chrysanthemol), whereas A. flavipes ATCC 1030 and ATCC 11013 showed complete enantioselectivity for the (+)-cis-chrysanthemol but a time-dependent enantioselectivity during oxidation of trans-chrysanthemol [oxidation of (+)-trans-chrysanthemol prior to (-)-trans-chrysanthemol]. The diastereoselectivity of all three microorganisms was time dependent, in that the trans-stereoisomers were oxidized prior to the cis-isomers.

ChemInform Abstract: Diastereoselective Oxidations of a Thioether Appended with a Neighboring Carboxylic Acid Group.

AbstractThe (methylthio)bicyclo(2.2.1)heptanecarboxylic acid (Ia) and the corresponding methyl carboxylate (Ib) are diastereoselectively oxidized by the bromine complex of 1,4‐diazabicyclo(2.2.2)octane to give the sulfoxides (IIa) and (IIIb) as the main products.

(+)-(3-Oxocamphorsulphonyl)oxaziridune as a highly stereoselective reagent for the oxidation of sulphides to chiral sulphoxides

The synthesis of the title oxaziridine and its application to the enantio- or diastereo-selective oxidation of sulphides to sulphoxides is described. Enantiomeric excesses up to 66% are observed, showing the reagent to be superior to most other oxidizing systems. The exceedingly mild reaction conditions (aprotic, neutral) allow the preparation of several chiral α-sulphinyl aldehydes. The properties of these compounds are discussed.

ChemInform Abstract: Diastereoselective Epoxidation of cis‐4‐Amino Allylic Alcohol with m‐Chloroperbenzoic Acid. An Efficient Synthesis of Statine.

AbstractThe protected amino alcohols (IV), prepared from the amino aldehydes (I), undergo diastereoselective oxidation with MCPBA to give the syn‐ epoxides (V) as the main products.

ChemInform Abstract: Synthesis of Configurationally Stable Allylic Sulfoxides via Diastereoselective Oxidation.

AbstractMCPBA oxidation of the sulfide (IIIa) yields the title sulfoxide (IV) which is configurationally stable at 20‐60 °C and epimerizes at 90 °C to give a 92/8 mixture of the sulfoxides (IV)/(V).

Diastereoselective oxidations of a thioether appended with a neighboring carboxylic acid group

Diastereoselective oxidations of a thioether appended with a neighboring carboxylic acid group

Synthesis of configurationally stable allylic sulphoxides via diastereoselective oxidation

Low temperature meta-chloroperbenzoic acid oxidation of allylic sulphide derived from (1S)-10-mercaptoisoborneol proceeds in a completely diastereoselective fashion to afford a configurationally stable allylic sulphoxide. The factors affecting the selectivity of the oxidation and the optical stability of the product are discussed.

ChemInform Abstract: Self‐Induced Diastereoselective Oxidation of Vinyl Sulfides Bearing a Chiral Hydroxy Group as a Way of Preparation of Optically Active Sulfinyl Dienophiles und Their Use in the Asymmetric Diels‐Alder Reaction to Cyclopentadiene.

AbstractDas Thiol (I) liefert definiert die En‐thioether (III), die mit verschiedenen Oxidationsmitteln überwiegend zu den Sulfoxiden (IV) sowie den Isomeren (V) reagieren.

Self-induced diastereoselective oxidation of vinyl sulfoxides bearing a chiral hydroxy group as a way of preparation of optically active sulfinyl dienophiles and their use in the asymmetric Diels-Alder reactions to cyclopentadiene

Self-induced diastereoselective oxidation of vinyl sulfoxides bearing a chiral hydroxy group as a way of preparation of optically active sulfinyl dienophiles and their use in the asymmetric Diels-Alder reactions to cyclopentadiene

Studies on enzymatic oxidation of secondary alcohols. Part V. Stereoselective oxidation of .BETA.-methyl-sec-alcohols and .ALPHA.-methylketones by Corynebacterium equi IFO 3730.

The enzyme system of Corynebacterium equi IFO 3730 catalyzed the diastereo-selective oxidation of β-methyl-sec-alcohols. For example, only the erythro isomer of 5-methyl-6-tetradecanol was oxidized to the corresponding ketone, the threo-alcohol remaining. Moreover, the resulting ketone was metabolized enantioselectively by the same microbe. Thus, it was possible to obtain optically active α-methylketones. This biochemical kinetic resolution method was applied for some 2-phenyl-3-alkanones, the expected chiral ketones of moderate to high optical purities being obtained. The degradation pathway was deduced to involve Baeyer-Villiger type oxidation, on the basis of the isolation of small amouts of α-phenylethyl alcohol and acetophenone.