Sharpless Asymmetric Dihydroxylation: An Impressive Gadget for the Synthesis of Natural Products: A Review

Mushtaq, Aqsa; Zahoor, Ameer Fawad; Bilal, Muhammad; Hussain, Syed Makhdoom; Irfan, Muhammad; Akhtar, Rabia; Irfan, Ali; Kotwica-Mojzych, Katarzyna

doi:10.3390/molecules28062722

Cited by 9 publications

(4 citation statements)

References 145 publications

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“…Conversely, to maintain cis -configuration for C3 and C4 in compounds 1b or 1d , we employed the Steglich reaction 11 for selective esterification of cis -diol. The Sharpless asymmetric dihydroxylation, 12 Mitsunobu, 13 and Steglich 14 reactions are well-established methods known for their reliability in terms of reactivity and chiral control.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric Synthesis of Four Stereoisomers of 2,2-Dimethyl-3-hydroxy-4-(1′-angeloyloxy)-6-acetylchromane from Ageratina grandifolia and Plausible Absolute Stereochemistry of the Natural Product

Oh,

Im,

Bae

et al. 2023

ACS Omega

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2,2-Dimethyl-3-hydroxy-4-(1′-angeloyloxy)-6-acetylchromane is a natural product isolated from Ageratina grandifolia that exhibits inhibitory activity against yeast α-glucosidase. Initially, its structure was proposed to be 4-hydroxy-3-((S)-1′-angeloyloxy-(R)-2′,3′-epoxy-3′-methyl)butylacetophenone with an epoxide, but the structure was later revised to 2,2-dimethyl-3R-hydroxy-4S-(1-angeloyloxy)-6-acetylchromane. In this study, we present a total synthesis of 2,2-dimethyl-3-hydroxy-4-(1′-angeloyloxy)-6-acetylchromane from A. gradifolia and its stereoisomers. The key features of their synthesis include Sharpless asymmetric dihydroxylation of a readily available benzopyran substrate and subsequent Mitsunobu or Steglich reaction to provide both cis- and trans-isomers with chiral control. The absolute stereochemistry of the natural product was determined to be 2,2-dimethyl-3S-hydroxy-4R-(1′-angeloyloxy)-6-acetylchromane based on optical rotations of the synthesized compounds. The absolute configuration of the synthesized stereoisomers was confirmed by Mosher ester analysis. In addition, we provided ECD spectra for the four stereoisomers, which will allow verification of the absolute configuration of the natural product. Synthesis of all four stereoisomers of 2,2-dimethyl-3-hydroxy-4-(1′-angeloyloxy)-6-acetylchromane would facilitate the exploration of their potential biomedical applications.

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Section: Resultsmentioning

confidence: 99%

Asymmetric Synthesis of Four Stereoisomers of 2,2-Dimethyl-3-hydroxy-4-(1′-angeloyloxy)-6-acetylchromane from Ageratina grandifolia and Plausible Absolute Stereochemistry of the Natural Product

Oh,

Im,

Bae

et al. 2023

ACS Omega

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“…This pathophysiological substrate justifies the use of TEM micrographs to study lens opacity. The compounds that form in the eye lens due to lipid peroxidation include dienes, a subclass of alkenes, chemical group readily reacted with OsO4, the employed TEM fixative, and contrasting agent [ 40 , 41 ].…”

Section: Discussionmentioning

confidence: 99%

Effects of Gold Nanoparticles Phytoreduced with Rutin in an Early Rat Model of Diabetic Retinopathy and Cataracts

Moldovan,

Păpurică,

Muntean

et al. 2023

Metabolites

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Diabetic retinopathy (DR) and cataracts (CA) have an early onset in diabetes mellitus (DM) due to the redox imbalance and inflammation triggered by hyperglycaemia. Plant-based therapies are characterised by low tissue bioavailability. The study aimed to investigate the effect of gold nanoparticles phytoreduced with Rutin (AuNPsR), as a possible solution. Insulin, Rutin, and AuNPsR were administered to an early, six-week rat model of DR and CA. Oxidative stress (MDA, CAT, SOD) was assessed in serum and eye homogenates, and inflammatory cytokines (IL-1 beta, IL-6, TNF alpha) were quantified in ocular tissues. Eye fundus of retinal arterioles, transmission electron microscopy (TEM) of lenses, and histopathology of retinas were also performed. DM was linked to constricted retinal arterioles, reduced endogen antioxidants, and eye inflammation. Histologically, retinal wall thickness decreased. TEM showed increased lens opacity and fibre disorganisation. Rutin improved retinal arteriolar diameter, while reducing oxidative stress and inflammation. Retinas were moderately oedematous. Lens structure was preserved on TEM. Insulin restored retinal arteriolar diameter, while increasing MDA, and amplifying TEM lens opacity. The best outcomes were obtained for AuNPsR, as it improved fundus appearance of retinal arterioles, decreased MDA and increased antioxidant capacity. Retinal edema and disorganisation in lens fibres were still present.

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“…The synthesis of chiral vicinal diols is of great relevance in synthetic chemistry. [49,50] One of the most common routes for their preparation is the Sharpless asymmetric dihydroxylation of alkenes with OsO 4 . [51] Another well studied reaction is the hydrolytic kinetic resolution of epoxides with Co-complexes.…”

Section: Entrymentioning

confidence: 99%

Chemoenzymatic Synthesis of Chiral Building Blocks Based on the Kinetic Resolution of Glycerol‐Derived Cyclic Carbonates

Terazzi,

Spannenberg,

von Langermann

et al. 2023

ChemCatChem

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The biocatalytic kinetic resolution of cyclic carbonates derived from glycerol is reported. A selection of 26 esterases and lipases was tested for the asymmetric hydrolysis of the model substrate (4‐(chloromethyl)‐1,3‐dioxolan‐2‐one) in aqueous medium. Among them, Pig Liver Esterase and Novozym® 435 showed the best selectivity with E = 38 and 49, respectively. Both enzymes were employed for the conversion of 12 glycerol derivatives under optimized conditions. The resolution of halogenated carbonates afforded the unconverted enantiomer in up to >99:1 er. Furthermore, Novozym® 435 was successfully recycled 10 times without significant loss of activity. Upscaling and isolation of a chiral carbonate was also demonstrated. Subsequent conversion of this chiral building block allowed the direct one‐pot synthesis of Guaifenesin, Mephenesin and Chlorphenesin in up to 89% yield and 94:6 er.

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Sharpless Asymmetric Dihydroxylation: An Impressive Gadget for the Synthesis of Natural Products: A Review

Cited by 9 publications

References 145 publications

Asymmetric Synthesis of Four Stereoisomers of 2,2-Dimethyl-3-hydroxy-4-(1′-angeloyloxy)-6-acetylchromane from Ageratina grandifolia and Plausible Absolute Stereochemistry of the Natural Product

Asymmetric Synthesis of Four Stereoisomers of 2,2-Dimethyl-3-hydroxy-4-(1′-angeloyloxy)-6-acetylchromane from Ageratina grandifolia and Plausible Absolute Stereochemistry of the Natural Product

Effects of Gold Nanoparticles Phytoreduced with Rutin in an Early Rat Model of Diabetic Retinopathy and Cataracts

Chemoenzymatic Synthesis of Chiral Building Blocks Based on the Kinetic Resolution of Glycerol‐Derived Cyclic Carbonates

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