Perfluoroalkylsulfonyl fluoride in organic synthesis: a facile synthesis of 17α-hydroxy steroids

Guo, Pengpeng; Ding, Kai

doi:10.1016/j.tetlet.2015.05.026

Cited by 8 publications

(4 citation statements)

References 22 publications

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“…[130] Important methods with a broad applicability to aliphatic, aromatic, and heterocyclic amines rely on the use of Ca(NTf 2 ) 2 in tert-amyl alcohol, [155] DABCO in THF, [156] DMAP, [157,158] and N-hydroxybenzotriazole (HOBt) with organosilicon additives (e. g. 1,1,3,3-tetramethyldisiloxane). [159] Synthesis of sulfonates via the SuFEx strategy included the use of both aliphatic alcohols (with Cs 2 CO 3 [160] or DBU [161] ) and phenols (with K 2 CO 3 , [162,163] Cs 2 CO 3 , [150,160,164,165] or DBU and NaHCO 3 [151] ). A general and efficient method applicable to both aliphatic and aromatic substrates was designed for O-silylated (TMS or TBDMS) derivatives including their reaction with sulfonyl fluorides in the presence of DBU in MeCN [166][167][168][169][170] or TBAF in THF.…”

Section: Applications In Synthetic and Medicinal Chemistrymentioning

confidence: 99%

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

2021

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Current medicinal chemistry relies heavily on the quality of building blocks, i. e. reagents used to introduce chemical diversity into the target molecules. The last decade witnessed an emergence of many novel (or well-overlooked old) chemotypes for drug discovery, which is related to adapting new synthetic methodologies, designing new sp 3 -enriched bioisosteres, paying attention to previously underrated (or even unwanted) structural motifs, or combination thereof. In this review with 532 references, a survey of selected chemotypes that emerged recently in medicinal chemistry is provided, with a focus on the synthesis of the corresponding building blocks. Thus, saturated (hetero)aliphatic boronates, sulfonyl fluorides, sulfinates, non-classical sp 3 -enriched benzene isosteres, bicyclic morpholine/piperidine/piperazine analogs, as well as gemdifluorinated cycloalkanes (as an example of emerging fluorinated motifs) are discussed.

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Section: Applications In Synthetic and Medicinal Chemistrymentioning

confidence: 99%

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

2021

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“…More recent literature has indicated that sulfonyl fluorides are viable as [ 18 F] deoxyfluorinating reagents (Takamatsu et al 2002 ; Guo and Ding 2015 ), and indeed some applicative value has been demonstrated by perfluorobutanesulfonyl fluoride (PFBS) (Vorbrüggen H. The conversion of primary or secondary alcohols with nonaflyl fluoride into their corresponding inverted fluorides. Synthesis (Stuttg) 2008 ; Bennua-Skalmowski and Vorbruggen 1995 ).…”

Section: Sulfur-[ 18 F] Fluorine Radiolabelled Reamentioning

confidence: 99%

Sulfur - fluorine bond in PET radiochemistry

Pascali

Matesic

Zhang

et al. 2017

EJNMMI radiopharm. chem.

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The importance of the sulfur-fluorine bond is starting to increase in modern medicinal chemistry literature. This is due to a better understanding of the stability and reactivity of this moiety depending on the various oxidation states of sulfur. Furthermore, several commercial reagents used for mild and selective fluorination of organic molecules are based on the known reactivity of S-F groups. In this review, we will show how these examples are translating into the 18F field, both for use as stable tags in finished radiopharmaceuticals and as mildly reactive fluoride-relay intermediates. Finally, we also discuss current opportunities where examples of non-radioactive S-F applications/chemistry may be translated into future 18F radiochemistry applications.

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“…For instance, reduction of 17‐ketosteroids with NaBH 4 produces exclusively 17β‐OH isomers due to the steric hindrance of the 18‐methyl group that blocks hydride attack from the upper face (Scheme 2). Therefore, when the product of interest is the 17α‐OH isomer, most efforts have been focused on inverting the configuration of 17β‐OH through Mitsunobu reactions, [7,8] or by the formation and displacement of sulfonyl ester derivatives [9–11] . However, both methods introduce further synthetic steps, including protection/deprotection reactions using expensive or non‐commercial reagents, and complicating product isolation and purification.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, when the product of interest is the 17α‐OH isomer, most efforts have been focused on inverting the configuration of 17β‐OH through Mitsunobu reactions,[ 7 , 8 ] or by the formation and displacement of sulfonyl ester derivatives. [ 9 , 10 , 11 ] However, both methods introduce further synthetic steps, including protection/deprotection reactions using expensive or non‐commercial reagents, and complicating product isolation and purification. As a result, the final yield obtained of the target 17α‐OH is usually very low.…”

Section: Introductionmentioning

confidence: 99%

One‐Step Chemo‐, Regio‐ and Stereoselective Reduction of Ketosteroids to Hydroxysteroids over Zr‐Containing MOF‐808 Metal‐Organic Frameworks

Mautschke

Xamena

2021

Chemistry A European J

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Zr-containing MOF-808 is a very promising heterogeneous catalyst for the selective reduction of ketosteroids to the corresponding hydroxysteroids through a Meerwein-Ponndorf-Verley (MPV) reaction. Interestingly, the process leads to the diastereoselective synthesis of elusive 17αhydroxy derivatives in one step, whereas most chemical and biological transformations produce the 17β-OH compounds, or they require several additional steps to convert 17β-OH into 17α-OH by inverting the configuration of the 17 center. Moreover, MOF-808 is found to be stable and reusable; it is also chemoselective (only keto groups are reduced, even in the presence of other reducible groups such as C=C bonds) and regioselective (in 3,17-diketosteroids only the keto group in position 17 is reduced, while the 3-keto group remains almost intact). The kinetic rate constant and thermodynamic parameters of estrone reduction to estradiol have been obtained by a detailed temperature-dependent kinetic analysis. The results evidence a major contribution of the entropic term, thus suggesting that the diastereoselectivity of the process is controlled by the confinement of the reaction inside the MOF cavities, where the Zr 4 + active sites are located.

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Perfluoroalkylsulfonyl fluoride in organic synthesis: a facile synthesis of 17α-hydroxy steroids

Cited by 8 publications

References 22 publications

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

Sulfur - fluorine bond in PET radiochemistry

One‐Step Chemo‐, Regio‐ and Stereoselective Reduction of Ketosteroids to Hydroxysteroids over Zr‐Containing MOF‐808 Metal‐Organic Frameworks

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