A gram‐scale synthesis of [3,4‐13C2,1α,7‐2H2]cortisone

Li, Zizhong; Heffner, Peter; Gong, Yumin

doi:10.1002/jlcr.1938

Cited by 4 publications

(4 citation statements)

References 43 publications

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“…The level of over‐deoxygenation may be controlled by switching the solvent from MeCN to CHCl 3 and by adjusting the reaction time and/or the amount of TMSI used (Scheme a) , . This methodology has been recently applied successfully to the gram‐scale synthesis of 13 C, 2 H‐labeled deoxygenated analogues of cortisone and cortisol . As shown in Scheme b, the TMSI‐mediated deoxygenation protocol was found to be compatible with “unactivated” free secondary hydroxy group ,.…”

Section: Iodine‐atom‐mediated Deoxygenationmentioning

confidence: 99%

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Metal‐Free Deoxygenation of α‐Hydroxy Carbonyl Compounds and Beyond

Pichon¹,

Hazelard²,

Compain³

2019

Eur J Org Chem

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Efficient deoxygenation methods are needed now more than ever in the chemist's toolbox to convert biomass‐derived molecules such as carbohydrates into useful chemicals. Late‐stage deoxygenation of drug candidates constitutes also an interesting option to fine tune their drug‐like properties. Metal‐based processes, as exemplified by the Barton–McCombie reaction, have long dominated the field. The development of metal‐free alcohol deoxygenation reactions represents however a challenge that has to be tackled to circumvent drawbacks associated with metal‐based reagents including cost and toxicity. Deoxygenation of alcohols may be assisted by the presence in α‐position of an electron‐withdrawing group. This review provides an overview of metal‐free methods that have been developed in the past decades for the direct, one‐step deoxygenation of α‐hydroxyl carbonyl compounds.

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Section: Iodine‐atom‐mediated Deoxygenationmentioning

confidence: 99%

“…This methodology has been recently applied successfully to the gram‐scale synthesis of 13 C, 2 H‐labeled deoxygenated analogues of cortisone and cortisol . As shown in Scheme b, the TMSI‐mediated deoxygenation protocol was found to be compatible with “unactivated” free secondary hydroxy group ,. [16b]…”

Section: Iodine‐atom‐mediated Deoxygenationmentioning

confidence: 99%

Metal‐Free Deoxygenation of α‐Hydroxy Carbonyl Compounds and Beyond

Pichon¹,

Hazelard²,

Compain³

2019

Eur J Org Chem

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“…In 2011, Li and co-workers reported a gram-scale synthesis of [3,4-13 C 2 ,1,7-2 H 2 ]-cortisone 2 from prednisone 45 (25 g/€224) in 9 steps and in 5% overall yield, based on the Turner sequence using [1,2-13 C 2 ]AcCl (Scheme 6). 31…”

Section: Syn Thesismentioning

confidence: 99%

Synthesis of 13C-Labeled Steroids

Dénès

Farard²,

Lebreton

2019

Synthesis

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Due to the wide spectrum of biological activities of steroids, the detection and quantification of steroidal residues in various biological materials are crucial for drug development, doping prevention, and environmental protection. In addition, the analytical technique of stable isotopic dilution (SID) by Liquid Chromatography-Mass Spectrometry (LC-MS) requires 13C-labeled steroids as standards to provide accurate and reproducible steroid quantification. In this context, the synthesis of 13C-labeled steroids is reviewed. The approaches based on partial synthesis starting from commercially available steroids have been, by far, the most commonly employed strategy.1 Introduction2 Hemisynthesis of 13C3-Labeled Steroids via Partial Degradation of the A Ring2.1 Degradation of the A Ring to an Enol Lactone2.1.1 Introduction of 13C Atom(s) via Claisen Condensation: Turner’s Strategy2.1.2 Introduction of 13C Atom(s) with 13C-Labeled 5-(Diethylphosphono)pentan-2-one Ethylene Ketal Based on the Fujimoto–Belleau Reaction2.2 Degradation of the A Ring and Introduction of 13C Atom(s) with [13C3]-1-(Triphenylphosphoranylidene)propan-2-one3 Construction of the A Ring from an α,β-Unsaturated Ketone with 13C-Labeled 1-Iodo-3,3-(ethylenedioxy)butane as Electrophile4 Construction of the A and B rings: Stork’s Strategy5 Hemisynthesis with Introduction of 13C Atom(s) in the C17 Side Chain6 Conclusion

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“…On the other hand, an internal standard was required for mass spectrometry for the detection or quantization of test materials in toxicology and metabolism studies. An isotopically labeled version of the test material that contains one or more stable isotopes ( 13 C, 15 N, 2 H or 18 O) can be used for this purpose …”

Section: Introductionmentioning

confidence: 99%

An overview of radio or stable isotope‐labeled cis‐neonicotinoid analogs

Liu

et al. 2012

Labelled Comp Radiopharmac

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To support the metabolism and toxicology study of cis‐neonicotinoids, radio or stable isotope was introduced into different sites of the key intermediate 2‐chloro‐5‐((2‐(nitromethylene)imidazolidin‐1‐yl)methyl)pyridine (6‐Cl‐PMNI). [3H2]‐ and [14C]‐label were successively prepared from initial materials NaB3H4 and [14C]‐nitromethane, respectively. Similarly, [D2]‐6‐Cl‐PMNI was prepared from NaBD4 in four steps, with 52.6% overall isotopic yield, and dual‐labeled [D2, 13C]‐target was obtained from NaBD4 and [13C]‐nitromethane, affording overall isotopic yield of 42.5%. Moreover, [14C2] was introduced from [U‐14C]‐ethylenediamine dihydrochloride in three steps, with a 58.3% overall chemical yield. Finally, typical labeled cis‐neonicotinoids paichongding and cycloxaprid were prepared and characterized. The methods were proved to have good generality in the synthesis of other cis‐neonicotinoids, and all results would be useful in metabolism studies of new cis‐neonicotinoids. Copyright © 2012 John Wiley & Sons, Ltd.

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A gram‐scale synthesis of [3,4‐¹³C_2,1α,7‐²H₂]cortisone

Cited by 4 publications

References 43 publications

Metal‐Free Deoxygenation of α‐Hydroxy Carbonyl Compounds and Beyond

Metal‐Free Deoxygenation of α‐Hydroxy Carbonyl Compounds and Beyond

Synthesis of 13C-Labeled Steroids

An overview of radio or stable isotope‐labeled cis‐neonicotinoid analogs

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