Addition-substitution reactions of 2-thio-3-chloroacrylamides with carbon, nitrogen, oxygen, sulfur and selenium nucleophiles

Kissane, Marie; Murphy, Maureen E.; O'Brien, Elisabeth; Chopra, Jay; Murphy, Linda; Collins, Stuart G.; Lawrence, Simon E.; Maguire, Anita R.

doi:10.1039/c0ob00805b

Cited by 17 publications

(25 citation statements)

References 40 publications

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“…11 Reaction of the b-chloroacrylamides with benzenethiol afforded the corresponding b-phenylthioacrylamides as the major product, as the Z-isomer exclusively for the sulfide derivatives and as a mixture of the E-and Z-isomers for the sulfoxide derivatives (Scheme 32).…”

Section: Addition Of Sulfur and Selenium Nucleophilesmentioning

confidence: 99%

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Stereoselective Synthesis of 2-Thio-3-Chloroacrylamides and Investigation of their Reactivity

Kissane¹,

Maguire²

2011

Synlett

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The stereoselective transformation of 2-thioamides to 2-thio-3-chloroacrylamides and the investigation of the scope of this transformation, including extension to ester and nitrile derivatives, is described. These highly functionalised acrylamide derivatives are synthetically versatile, and their reactivity has been investigated in a wide range of transformations, including chemoselective oxidation to the racemic sulfoxide or sulfone, and enantioselective and diastereoselective oxidation to the sulfoxides. The 2-thio-3-chloroacrylamides were found to be very effective Michael acceptors in nucleophilic addition/substitution reactions, dienophiles in DielsAlder cycloadditions, and dipolarophiles in 1,3-dipolar cycloadditions. The level of oxidation at sulfur was found to strongly influence the reactivity. This account summarises synthetic and mechanistic aspects of the research programme focussed on the synthesis and reactivity of 2-thio-3-chloroacrylamides in our research group over the past decade.

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Section: Addition Of Sulfur and Selenium Nucleophilesmentioning

confidence: 99%

“…11 It was found that substitution at the b-position is possible using carbon nucleophiles ranging from reactive systems to stabilised enolates. The yields are modest in most instances, but the reactions proceed with good retention of stereochemistry, and generally the monosubstituted adducts can be isolated.…”

Section: Addition Of Carbon Nucleophilesmentioning

confidence: 99%

Stereoselective Synthesis of 2-Thio-3-Chloroacrylamides and Investigation of their Reactivity

Kissane¹,

Maguire²

2011

Synlett

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“…The predominant site of reactivity is at the electrophilic β-carbon, which results from the combined influence of the amide and chloro substituents, mitigating the electron-donating effect of the sulfide moiety. Nucleophilic substitution [4], Diels–Alder reactions [5] and 1,3-dipolar cycloadditions [6–9], and oxidation of the sulfide group [10–12] are among a wide array of transformations which have been successfully applied to these compounds (Scheme 1). …”

Section: Introductionmentioning

confidence: 99%

Development of a continuous process for α-thio-β-chloroacrylamide synthesis with enhanced control of a cascade transformation

Dennehy¹,

Cacheux²,

Deadman³

et al. 2016

Beilstein J. Org. Chem.

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A continuous process strategy has been developed for the preparation of α-thio-β-chloroacrylamides, a class of highly versatile synthetic intermediates. Flow platforms to generate the α-chloroamide and α-thioamide precursors were successfully adopted, progressing from the previously employed batch chemistry, and in both instances afford a readily scalable methodology. The implementation of the key α-thio-β-chloroacrylamide casade as a continuous flow reaction on a multi-gram scale is described, while the tuneable nature of the cascade, facilitated by continuous processing, is highlighted by selective generation of established intermediates and byproducts.

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“…18 The resulting -morpholinoacrylamides contain an enamine functionality, and during chromatographic purification with a number of these -morpholinoacrylamides, partial or complete hydrolysis of the acid labile enamine group was observed (Scheme 3). For example, partial hydrolysis of the -morpholinoacrylamide 4a on silica gel led to a 3:1 mixture of the keto and enol tautomers of 5a, while hydrolysis of 4b and 4c led to the enol tautomers 5b and 5c exclusively.…”

Section: Resultsmentioning

confidence: 99%

“…[15][16][17] The synthetic potential of the -chloroacrylamides as Michael acceptors in nucleophilic addition/substitution reactions has also been investigated, including addition of morpholine to yield -enaminoamides. 18 In early experiments, partial hydrolysis was seen on purification of the morpholine adducts by chromatography on silica gel, hence showing that the -enaminoamides could be hydrolysed (Scheme 1).…”

Section: 3mentioning

confidence: 99%

Selective β-oxidation of α-sulfanyl amides

et al. 2011

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Addition-substitution reactions of 2-thio-3-chloroacrylamides with carbon, nitrogen, oxygen, sulfur and selenium nucleophiles

Cited by 17 publications

References 40 publications

Stereoselective Synthesis of 2-Thio-3-Chloroacrylamides and Investigation of their Reactivity

Stereoselective Synthesis of 2-Thio-3-Chloroacrylamides and Investigation of their Reactivity

Development of a continuous process for α-thio-β-chloroacrylamide synthesis with enhanced control of a cascade transformation

Selective β-oxidation of α-sulfanyl amides

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