Preparation of (25)- and (25)-26-functionalized steroids as tools for biosynthetic studies of cholic acids

Хрипач, В. А.; Жабинский, В. Н.; Konstantinova, Olga V.; Khripach, N. B.; Antonchick, A. V.; Antonchick, Andrey P.; Schneider, Bernd

doi:10.1016/j.steroids.2005.02.014

Cited by 25 publications

(19 citation statements)

References 47 publications

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“…Recently, successful use of NaClO 2 catalyzed by TEMPO and NaClO for oxidation of alcohols suggested that a selective oxidation of primary hydroxy group to its carboxyl group without oxidizing a secondary hydroxy group might be feasible (Anelli, Biffi, Montanari, & Quici, ; de Nooy, Besemer, & van Bekkum, ; Khripach et al, ; Zhao et al, ). Expectedly, mild reaction of 8a and 8b with NaClO 2 in the presence of the coreagents resulted in selective oxidation of the primary 24‐hydroxy group to afford the desired 3α,11α‐dihydroxy and 3α,7α,11α‐trihydroxy acids ( 1a and 1b ) in excellent isolated yields of 84 and 82%, respectively.…”

Section: Resultsmentioning

confidence: 99%

Chemical Synthesis of Rare Natural Bile Acids: 11α‐Hydroxy Derivatives of Lithocholic and Chenodeoxycholic Acids

Namegawa

Iida

Omura

et al. 2018

Lipids

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A method for the preparation of 11α-hydroxy derivatives of lithocholic and chenodeoxycholic acids, recently discovered to be natural bile acids, is described. The principal reactions involved were (1) elimination of the 12α-mesyloxy group of the methyl esters of 3α-acetate-12α-mesylate and 3α,7α-diacetate-12α-mesylate derivatives of deoxycholic acid and cholic acid with potassium acetate/hexamethylphosphoramide; (2) simultaneous reduction/hydrolysis of the resulting △ -3α-acetoxy and △ -3α,7α-diacetoxy methyl esters with lithium aluminum hydride; (3) stereoselective 11α-hydroxylation of the △ -3α,24-diol and △ -3α,7α,24-triol intermediates with B H /tetrahydrofuran (THF); and (4) selective oxidation at C-24 of the resulting 3α,11α,24-triol and 3α,7α,11α,24-tetrol to the corresponding C-24 carboxylic acids with NaClO catalyzed by 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO) and NaClO. In summary, 3α,11α-dihydroxy-5β-cholan-24-oic acid and 3α,7α,11α-trihydroxy-5β-cholan-24-oic acid have been synthesized and their nuclear magnetic resonance (NMR) spectra characterized. These compounds are now available as reference standards to be used in biliary bile acid analysis.

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Section: Resultsmentioning

confidence: 99%

Chemical Synthesis of Rare Natural Bile Acids: 11α‐Hydroxy Derivatives of Lithocholic and Chenodeoxycholic Acids

Namegawa

Iida

Omura

et al. 2018

Lipids

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“…Recently successful use of sodium chlorite (NaClO 2 ) catalyzed by 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO) and sodium hypochlorite (NaClO; bleach) for oxidation of alcohols [26][27][28][29][30] suggested that a selective oxidation of a primary hydroxyl group to its carboxyl group without oxidizing a secondary hydroxyl group might be feasible. As expected, mild reaction of 9a and b with TEMPO in the presence of the co-reagents resulted in successful selective oxidation of the primary 24-hydroxyl group to afford the desired 3α,9α-dihydroxy and 3α,7α,9α-trihydroxy acids (1a; 58%, 1b; 71%), respectively.…”

Section: )mentioning

confidence: 99%

Chemical Synthesis of Uncommon Natural Bile Acids: The 9α-Hydroxy Derivatives of Chenodeoxycholic and Lithocholic Acids

Iida

Namegawa

Nakane

et al. 2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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The chemical synthesis of the 9α-hydroxy derivatives of chenodeoxycholic and lithocholic acids is reported. For initiating the synthesis of the 9α-hydroxy derivative of chenodeoxycholic acid, cholic acid was used; for the synthesis of the 9α-hydroxy derivative of lithocholic acid, deoxycholic acid was used. The principal reactions involved were (1) decarbonylation of conjugated 12-oxo-Δ 9(11) -derivatives using in situ generated monochloroalane (AlH 2 Cl) prepared from LiAlH 4 and AlCl 3 , (2) epoxidation of the deoxygenated Δ 9(11) -enes using m-chloroperbenzoic acid catalyzed by 4,4′-thiobis-(6-tert-butyl-3-methylphenol), (3) subsequent Markovnikov 9α-hydroxylation of the Δ 9(11) -enes with AlH 2 Cl, and (4) selective oxidation of the primary hydroxyl group at C-24 in the resulting 3α,9α,24-triol and 3α,7α,9α,24-tetrol to the corresponding C-24 carboxylic acids using sodium chlorite (NaClO 2 ) in the presence of a catalytic amount of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO) and sodium hypochlorite (NaOCl). The 1 H-and 13 C-NMR spectra are reported. The 3α,7α,9α-trihydroxy-5β-cholan-24-oic acid has been reported to be present in the bile of the Asian bear, and its 7-deoxy derivative is likely to be a bacterial metabolite. These bile acids are now available as authentic reference standards, permitting their identification in vertebrate bile acids.

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“…EBL is recognized as a potential compound in the cure of human immunodeficiency virus (HIV) infection and other associated conditions in addition to help in the reduction of blood serum cholesterol for remedial and prophylactic applications in medicine and specialized nutrition. The applications of this steroidal plant hormone helped in recovering blood cholesterol and gave a new direction in the treatment of infections caused by HIV [98,99]. Antiherpetic activity of synthetic analogues of BRs such as (22S,23S)-3β-bromo-5α, 22, 23-trihydroxystigmastan-6-one (1)…”

Section: Antiherpetic Activitiesmentioning

confidence: 99%

Therapeutic Potential of Brassinosteroids in Biomedical and Clinical Research

Kohli

Bhardwaj

et al. 2020

Biomolecules

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Steroids are a pivotal class of hormones with a key role in growth modulation and signal transduction in multicellular organisms. Synthetic steroids are widely used to cure large array of viral, fungal, bacterial, and cancerous infections. Brassinosteroids (BRs) are a natural collection of phytosterols, which have structural similarity with animal steroids. BRs are dispersed universally throughout the plant kingdom. These plant steroids are well known to modulate a plethora of physiological responses in plants leading to improvement in quality as well as yield of food crops. Moreover, they have been found to play imperative role in stress-fortification against various stresses in plants. Over a decade, BRs have conquered worldwide interest due to their diverse biological activities in animal systems. Recent studies have indicated anticancerous, antiangiogenic, antiviral, antigenotoxic, antifungal, and antibacterial bioactivities of BRs in the animal test systems. BRs inhibit replication of viruses and induce cytotoxic effects on cancerous cell lines. Keeping in view the biological activities of BRs, this review is an attempt to update the information about prospects of BRs in biomedical and clinical application.

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Preparation of (25)- and (25)-26-functionalized steroids as tools for biosynthetic studies of cholic acids

Cited by 25 publications

References 47 publications

Chemical Synthesis of Rare Natural Bile Acids: 11α‐Hydroxy Derivatives of Lithocholic and Chenodeoxycholic Acids

Chemical Synthesis of Rare Natural Bile Acids: 11α‐Hydroxy Derivatives of Lithocholic and Chenodeoxycholic Acids

Chemical Synthesis of Uncommon Natural Bile Acids: The 9α-Hydroxy Derivatives of Chenodeoxycholic and Lithocholic Acids

Therapeutic Potential of Brassinosteroids in Biomedical and Clinical Research

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