Multigram scale synthesis of 3,4- and 3,6-dihydro-2<i>H</i>-thiopyran 1,1-dioxides and features of their NMR spectral behavior

Chabanenko, Roman M.; Mykolenko, Svitlana; Kozirev, Eugene K.; Palchykov, Vitalii A.

doi:10.1080/00397911.2018.1486427

Cited by 11 publications

(9 citation statements)

References 13 publications

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“…We start our study from the synthesis of alcohols 3a-d based on commercially available ketones 4a-c and 3,4-epoxysulfolane 4d as described earlier (Chabanenko et al 2018;) (Scheme 2). The reaction of alcohols 3a-d with trichloroacetyl isocyanate following the hydrolysis of trichloroacetyl protecting group with potassium carbonate in methanol at room temperature furnished ve-and sixmembered ring sulfone carbamates 5a-d in 78-88% yield.…”

Section: Resultsmentioning

confidence: 99%

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Rh-catalyzed cyclization of carbamates–synthesis of a new heterocyclic system: tetrahydro-3H-4-oxa-2-thia-2b-azacyclopropa[cd]pentalen-3-one 2,2-dioxide

Dil,

Kozyriev,

Palchykov

2023

Chem. Pap.

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A simple method for the synthesis of ve-and six-membered ring sulfone carbamates was elaborated.The method includes reaction of the corresponding starting alcohols with trichloroacetyl isocyanate following the hydrolysis of trichloroacetyl protecting group with potassium carbonate in methanol.Rh 2 (OAc) 4 catalyzed cyclization of carbamates was investigated. It was shown that carbamates with saturated sulfone moiety tend to give products of elimination of carbamic acid (corresponding unsaturated sulfones) due to high acidity of C-H bond in α-position of sulfone ring. Unsaturated sulfone carbamate (1,1-dioxido-2,3-dihydrothiophen-3-yl carbamate) in similar reaction conditions afforded new heterocyclic system con rmed by 2D NMR: tetrahydro-3H-4-oxa-2-thia-2b-azacyclopropa[cd]pentalen-3one 2,2-dioxide. This result can be explained by more favorable aziridination of the double C=C bond by the nitrenoid intermediate compared to the elimination pathway. In silico pharmacological pro le of new heterocyclic compound was evaluated. The compound showed good ADME and acute toxicity properties and high probability level of anticancer activity for prostate carcinoma cell line PC-3.

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Section: Resultsmentioning

confidence: 99%

“…Retention factors (R f ) are reported along with the solvent system used in parentheses. The starting alcohols 3a-d were synthesized as reported (Chabanenko et al 2018;).…”

Section: Methodsmentioning

confidence: 99%

Rh-catalyzed cyclization of carbamates–synthesis of a new heterocyclic system: tetrahydro-3H-4-oxa-2-thia-2b-azacyclopropa[cd]pentalen-3-one 2,2-dioxide

Dil,

Kozyriev,

Palchykov

2023

Chem. Pap.

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“…Although such a motif is a prime target for Diels–Alder approaches, accessibility and stability of the reactants, as well as polarity matching, is not always trivial. For example, access to olefinic sulfone 5 can be laborious (previously reported in 7 steps), [21] whereas electrochemical decarboxylation allows its preparation in a single step from the commercially available acid ($5.4/g). Similarly, the synthesis of 4‐aminocyclohexene derivatives 6 and 7 from a readily available carboxylic acid ($4.8/g, free amine) also exemplifies the potential of this protocol to circumvent a cumbersome Diels–Alder/Curtius rearrangement sequence [8,22] .…”

Section: Figurementioning

confidence: 99%

Scalable Electrochemical Decarboxylative Olefination Driven by Alternating Polarity**

Garrido‐Castro,

Hioki,

Kusumoto

et al. 2023

Angew Chem Int Ed

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A mild, scalable (kg) metal‐free electrochemical decarboxylation of alkyl carboxylic acids to olefins is disclosed. Numerous applications are presented wherein this transformation can simplify alkene synthesis and provide alternative synthetic access to valuable olefins from simple carboxylic acid feedstocks. This robust method relies on alternating polarity to maintain the quality of the electrode surface and local pH, providing a deeper understanding of the Hofer‐Moest process with unprecedented chemoselectivity.

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“…The authors have cited additional references within the Supporting Information. [29][30][31][32][33][34][35][36][37][38][39] MA was employed by Asahi Kasei Pharma Corporation. We thank Dr Adrian C. Whitwood for X-ray crystallography.…”

Section: Supporting Informationmentioning

confidence: 99%

α‐Functionalisation of Cyclic Sulfides Enabled by Lithiation Trapping

Seling,

Atobe,

Kasten

et al. 2023

Angewandte Chemie

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A general and straightforward procedure for the lithiation trapping of cyclic sulfides such as tetrahydrothiophene, tetrahydrothiopyran and a thiomorpholine is described. Trapping with a wide range of electrophiles is demonstrated, leading to more than 50 diverse α‐substituted saturated sulfur heterocycles. The methodology provides access to a range of α‐substituted cyclic sulfides that are not easily synthesised by the currently available methods.

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Multigram scale synthesis of 3,4- and 3,6-dihydro-2H-thiopyran 1,1-dioxides and features of their NMR spectral behavior

Cited by 11 publications

References 13 publications

Rh-catalyzed cyclization of carbamates–synthesis of a new heterocyclic system: tetrahydro-3H-4-oxa-2-thia-2b-azacyclopropa[cd]pentalen-3-one 2,2-dioxide

Rh-catalyzed cyclization of carbamates–synthesis of a new heterocyclic system: tetrahydro-3H-4-oxa-2-thia-2b-azacyclopropa[cd]pentalen-3-one 2,2-dioxide

Scalable Electrochemical Decarboxylative Olefination Driven by Alternating Polarity**

α‐Functionalisation of Cyclic Sulfides Enabled by Lithiation Trapping

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