A Recent Progress for the Synthesis of Thiocarboxylates

Wang, Xi; Dong, Zhi‐Bing

doi:10.1002/ejoc.202200452

Cited by 14 publications

(4 citation statements)

References 141 publications

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“…Another well-developed technique for the synthesis of thioethers is the transition metal-catalyzed cross-coupling reaction . The traditional approach for thioesters is the direct coupling of thiols with activated carboxylic acid . Up to now, both of these conventional multistep methods have used thiols as the thiol source, which are often restricted due to their unpleasant odors, high cost, and instability .…”

mentioning

confidence: 99%

Organophosphorus-Catalyzed “Dual-Substrate Deoxygenation” Strategy for C–S Bond Formation from Sulfonyl Chlorides and Alcohols/Acids

Sun

Liu

et al. 2023

J. Org. Chem.

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A green method to construct C–S bonds using sulfonyl chlorides and alcohols/acids via a PIII/PVO catalytic system is reported. The organophosphorus-catalyzed umpolung reaction promotes us to propose the “dual-substrate deoxygenation” strategy. Herein, we adopt the “dual-substrate deoxygenation” strategy, which achieves the deoxygenation of sulfonyl chlorides and alcohols/acids to synthesize thioethers/thioesters driven by PIII/PVO redox cycling. The catalytic method represents an operationally simple approach using stable phosphine oxide as a precatalyst and shows broad functional group tolerance. The potential application of this protocol is demonstrated by the late-stage diversification of drug analogues.

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confidence: 99%

Organophosphorus-Catalyzed “Dual-Substrate Deoxygenation” Strategy for C–S Bond Formation from Sulfonyl Chlorides and Alcohols/Acids

Sun

Liu

et al. 2023

J. Org. Chem.

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“…In an analogous fashion, reaction with hydrogen sulfide gives cyanothioacetate 7 and its acid 8 which are relevant, biologically active compounds. 42 Treatment of the cyanoketene anion with ammonia led to the formation of compound 9 in an excellent 87% yield. To the best of our knowledge, this highly functionalized compound has never been reported before, but offers various sites for further transformations.…”

Section: Reactivity Of the Cyanoketene Anionmentioning

confidence: 99%

The Cyanoketene Anion [NC3O]-

Krischer,

Swamy,

Feichtner

et al. 2024

Preprint

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Cumulenes and heterocumulenes with three or more cumulative multiple bonds are usually reactive species, that serve as valuable building blocks to more complex molecules but tend to isomerize or cyclize and therefore are difficult to isolate. Until to date, numerous (hetero)cumulenes have been detected in the interstellar medium and are assumed to be important intermediates in prebiotic chemistry, in particular when containing nitrogen and oxygen functionalities. Using a mild ligand exchange reaction at carbon in metalated ylides, we have now succeeded in the synthesis and gram-scale isolation of the so far elusive cyanoketene anion, [NC3O]-. Despite its assumed cumulene-like structure and the delocalization of the negative charge across the whole 5-atomic molecule, it features a bent geometry in solid state with a nucleophilic central carbon atom. Computational studies reveal an ambiguous bonding situation in the anion, which can only be illustrated by a combination of different resonance structures. Nonetheless, the anion features a remarkable stability, thus allowing the storage of its potassium salt and its application as highly functional synthetic building block. The cyanoketene anion readily reacts with a series of small molecules to more complex organic compounds including industrially valuable compounds such as cyanoacetate. This work demonstrates that reactive species found in the interstellar medium can be made accessible by novel synthesis methods and open up new pathways to more complex compounds through reaction with small molecules, an atom economic strategy sought in sustainable chemistry.

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“…[3][4][5][6][7][8][9][10][11][12][13][14] Drawing continuous inspiration from nature, researchers are increasingly directing their focus towards thioesters, sulfur-based counterparts of oxoesters, a subject that has garnered considerable attention in recent literature reviews. 15,16 Naturally occurring compounds featuring a thioester moiety (Figure 1, chart a) predominantly serve as intermediates in the synthesis of various other compounds, including acetyl coenzyme A, a carrier of acyl groups and a substrate in the Szent-Györgyi-Krebs cycle. 17 Among bioactive compounds, Formicin A stands as an antitumor antibiotic 18 , and distinctions can be made for glucocorticoid inhalers used in asthma treatment, such as Fluticasone or its propionic acid ester.…”

Section: Introductionmentioning

confidence: 99%

Betaketothioesters in Organocatalysis: Harnessing Nucleophilic Reactivity, the Fluorophobic Effect, and Expanding the Substrate Repertoire

Dajek,

Kubiak,

Bąkowicz

et al. 2023

Preprint

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The use of thioesters as nucleophiles marks a considerable change in organic synthesis. This new method, propelled by gentle enolization with minimal catalyst loading, results in enantiomeric excesses surpassing 95% under ambient conditions, accomplishing total conversion in merely 6 hours. Remarkably, this method eliminates the need for additional functional groups in nitroalkenes for efficient chirality transfer from the organocatalyst. The exceptional reactivity of thioesters, combined with their water tolerance, enables reactions utilizing the hydrophobic effect, resulting in reaction times as short as 15 minutes and products with slightly enhanced stereoselectivity compared to analogous reactions in dichloromethane. Additionally, reactions performed in perfluorinated solvents outpace their homogenous counterparts in organic solvents, delivering products in shorter time with comparable stereoselectivity. This work highlights the rare utilization of the fluorous effect in organocatalysis. Simple squaramides also exhibit remarkable catalytic activity in the reactions of beta-keto thioesters with alpha-bromo nitroalkenes. As little as 0.1 mol% of the catalyst leads to product formation with an 86% yield (qNMR) and 93% enantiomeric excess. Upscaling the reaction does not significantly affect the enantiomeric excess but leads to a slight decrease in yield from 82% to 77%. It has been demonstrated that thioesters react more rapidly than their ketoester counterparts, and the two-step reaction leading to dihydrofuran ring closure is entirely accomplished by extending the reaction time, eliminating the need for additional base. The examples presented here expand the range of substrates derived from carboxylic acid esters in catalytic reactions, suggesting the potential for the synthesis of challenging reactions in analogues of alkoxyl esters.

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A Recent Progress for the Synthesis of Thiocarboxylates

Cited by 14 publications

References 141 publications

Organophosphorus-Catalyzed “Dual-Substrate Deoxygenation” Strategy for C–S Bond Formation from Sulfonyl Chlorides and Alcohols/Acids

Organophosphorus-Catalyzed “Dual-Substrate Deoxygenation” Strategy for C–S Bond Formation from Sulfonyl Chlorides and Alcohols/Acids

The Cyanoketene Anion [NC3O]-

Betaketothioesters in Organocatalysis: Harnessing Nucleophilic Reactivity, the Fluorophobic Effect, and Expanding the Substrate Repertoire

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