Exploring the potential of the β-thiolactones in bioorganic chemistry

Aubry, Sylvain; Sasaki, Kaname; Eloy, Laure; Aubert, Geneviève; Retailleau, Pascal; Cresteil, Thierry; Crich, David

doi:10.1039/c1ob05967j

Cited by 17 publications

(19 citation statements)

References 90 publications

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“…Recognizing that by incorporation of a thioester, we are introducing a thiol in protected form, we were able to transform A13 to 5‐mercaptopentanoic acid ( F1 ) by subjecting the product of the hydrothiolation reaction to an acidic workup and affording the free thiol in 92 % yield (Scheme 4 A). This thiol can then easily be converted to a δ‐thiolactone by Steglich thiolactonization, delivering a class of compound important in numerous fields [17, 18, 69–75] . In addition to this, we also attempted the hydrothiolation of an alkyne (thiol‐yne reaction) [76, 77] .…”

Section: Figurementioning

confidence: 99%

Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes

McCourt

Scanlan

2020

Chemistry A European J

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Am ild, metal-free, atmospheric oxygen-mediated radical hydrothiolation of alkenes (and alkyne) is reported. Av ariety of sulfur containingm otifs including alkanethiols,t hiophenols and thioacidsu ndergo an atmospheric oxygen-mediated radicalh ydrothiolation reaction with ap lethora of alkenes in good yield with excellent functional group compatibility,t ypically with short reaction times to furnisharange of functionalized products. Biomoleculesp rovedt olerant to the conditions and the procedure is robust and easily executable requiring no specialized equipment. Concise mechanistic studies confirm the process proceeds throughr adical intermediates in at hiol-ene reaction manifold. Them ethodology offers an efficient "green" approach for thiol-ene mediated "click" ligation and am ilder alternative to thermally initiated hydrothiolation processes.

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Section: Figurementioning

confidence: 99%

Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes

McCourt

Scanlan

2020

Chemistry A European J

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“…Thiolactones are endocyclic sulfur‐containing analogues of lactones and represent a fascinating class of heterocyclic compounds. Less abundant than lactones, this family of compounds has been identified as having potential impact in numerous fields, including chemical biology, medicinal chemistry, drug discovery, and materials science . Interest in these compounds stems from the unique reactivity bestowed upon them by the incorporation of the sulfur atom, allowing them to undergo chemical, and biochemical reactions not available to lactones.…”

Section: Thiolactonesmentioning

confidence: 99%

“…Less abundant than lactones, this family of compounds has been identified as having potential impact in numerous fields, including chemical biology, medicinal chemistry, drug discovery, and materials science. [64][65][66][67][68][69] Interest in these compounds stems from the unique reactivity bestowed upon them by the incorporation of the sulfur atom, allowing them to undergo chemical, and biochemical reactions not available to lactones. Thiolactones have proven highly valuable in synthesis and biology.…”

Section: Thiolactonesmentioning

confidence: 99%

5‐exo versus 6‐endo Thiyl‐Radical Cyclizations in Organic Synthesis

McCourt

Scanlan

2019

Helvetica Chimica Acta

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Since the discovery of the radical mediated thiol‐ene and thiol‐yne reactions, these reactions have been employed in an intramolecular manner for the synthesis of sulfur‐containing heterocycles. Although closely related on a mechanistic basis, the thiol‐ene and thiol‐yne cyclization can differ greatly in regioselectivity and product distribution, with the thiol‐ene process being more predictable and thus attracting greater utilization. Herein, we review intramolecular thiyl‐radical addition reactions and the factors leading to the observed regioselectivity in examples in which both the 5‐exo and 6‐endo mode of cyclization are feasible. We highlight the applications of these important reactions for organic synthesis in the recent literature.

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“…Fortunately, β-thiolactones can react with nucleophiles, including both acylating and alkylating abilities. This feature makes β-thiolactones a novel class of compounds with promising potential in bioorganic chemistry [9,10]. The most recent literature examples compare the reactivity of β-thiolactones and β-lactones.…”

Section: Introductionmentioning

confidence: 99%

Ring Expansions of β-Lactams and β-(thio)lactones

Alcaide

Almendros

Aragoncillo

2015

Topics in Heterocyclic Chemistry

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The skeleton of β-lactams and β-lactones is present in biologically active compounds. For example, the β-lactam ring is present in classical antibiotics such as penicillins and cephalosporins. On the other hand, there are several natural products containing a β-lactone moiety, with interesting inhibitory activity. In addition, both fragments are very useful synthetic intermediates for the preparation of cyclic and acyclic compounds. The ring strain present in both motifs is involved in this versatile reactivity. This chapter is devoted to the synthesis of five-to sevenmembered heterocycles by ring expansion of β-lactams and β-lactones. Different methodologies have been described, and the mechanism for the formation of the products has been discussed. In addition, the applicability of some of the processes has been demonstrated by the synthesis of fragments of natural or biologically relevant compounds. The contributions presented in this chapter have been selected mainly from the developments achieved in the last decade.

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Exploring the potential of the β-thiolactones in bioorganic chemistry

Cited by 17 publications

References 90 publications

Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes

Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes

5‐exo versus 6‐endo Thiyl‐Radical Cyclizations in Organic Synthesis

Ring Expansions of β-Lactams and β-(thio)lactones

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