Asymmetric synthesis of tertiary thiols and thioethers

Clayden, Jonathan; MacLellan, Paul

doi:10.3762/bjoc.7.68

Cited by 184 publications

(93 citation statements)

References 79 publications

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“…Furthermore, thione 22 , which could easily be synthesized from the parent ketone, was also suitable for this coupling process. The highly enantioselective preparation of tertiary thiol 23 (> 10:1 d.r., 96% ee) using our strategy represents a synthetically valuable advance, given that enantioenriched thiols are prevalent structural motifs in a variety of small molecule therapeutics and only a handful of enantioselective methods are available for their preparation (36). …”

mentioning

confidence: 99%

Copper-catalyzed asymmetric addition of olefin-derived nucleophiles to ketones

Yang

Perry

Lü

et al. 2016

Science

251

134

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Enantioenriched alcohols found in an array of bioactive natural products and pharmaceutical agents are often synthesized by asymmetric nucleophilic addition to carbonyls. However, this approach generally shows limited functional group compatibility, requiring the use of preformed organometallic reagents in conjunction with a stoichiometric or sub-stoichiometric amount of chiral controller to deliver optically active alcohols. Herein we report a copper-catalyzed strategy for the stereoselective nucleophilic addition of propargylic and other alkyl groups to ketones using easily accessible (poly)unsaturated hydrocarbons as latent carbanion equivalents. Our method features the catalytic generation of highly enantioenriched organocopper intermediates and their subsequent diastereoselective addition to ketones, allowing for the effective construction of highly substituted stereochemical dyads with excellent stereocontrol. Moreover, this process is general, scalable, and occurs at ambient temperature.

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mentioning

confidence: 99%

Copper-catalyzed asymmetric addition of olefin-derived nucleophiles to ketones

Yang

Perry

Lü

et al. 2016

Science

251

134

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“…Diverse methods are known for their preparation [1], and in recent years, asymmetric syntheses of thiols have been studied extensively [2,3]. It is well known that many thiols are biologically active substances [4] and some of them are of special interest as odorous compounds [5].…”

Section: Introductionmentioning

confidence: 99%

The unusual influence of hetaryl groups on the direct conversion of some secondary alcohols into thiols with Lawesson’s reagent: elucidation of the reaction mechanism

Mlostoń

Hamera-Fałdyga

Celeda

et al. 2017

Journal of Sulfur Chemistry

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A series of hetaryl-substituted methanols were used for direct conversion into the corresponding thiols by treatment with Lawesson's reagent in boiling toluene. Unexpectedly, the respective sulfides were formed exclusively. In the case of chiral alcohols, the sulfides were obtained as 1:1-mixtures of meso-and dl-diastereoisomers. In contrast to hetaryl-substituted alcohols, the analogous protocol applied for benzhydryl alcohol led to a mixture of the expected secondary thiol and a bis(diphenylmethyl) trithiophosphonate. Finally, the analogous reactions with ferrocenyl(phenyl)methanol and diferrocenylmethanol, respectively, led to the corresponding thiols in good yield. Unexpectedly, the respective sulfides were formed exclusively. In the case of chiral alcohols, the sulfides were obtained as 1:1-mixtures of meso-and dl-diastereoisomers.In contrast to hetaryl-substituted alcohols, the analogous protocol applied for benzhydryl alcohol led to a mixture of the expected secondary thiol and a bis(diphenylmethyl) trithiophosphonate. Finally, the analogous reactions with ferrocenyl(phenyl)methanol and diferrocenylmethanol, respectively, led to the corresponding thiols in good yield. CONTACT

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“…In the past few decades, diverse competent asymmetric strategies have been established to access these chiral entities [1–4]. Among them, catalytic asymmetric functionalization of S -containing prochiral carbon centers can be considered to be one of the most efficient and expedient approach [1–4]. The development of novel S -containing substrates has therefore attracted the attention of chemists [1–4].…”

Section: Introductionmentioning

confidence: 99%

“…Among them, catalytic asymmetric functionalization of S -containing prochiral carbon centers can be considered to be one of the most efficient and expedient approach [1–4]. The development of novel S -containing substrates has therefore attracted the attention of chemists [1–4]. For example in 2013, Palomo and co-workers introduced 5 H -thiazol-4-ones as a new class of sulfur-containing pro-nucleophiles in a highly enantio- and diastereoselective conjugate addition to nitroalkenes, providing α,α-disubstituted α-mercapto carboxylic acids [5].…”

Section: Introductionmentioning

confidence: 99%