Synthesis of ferrocenyl- and hetaryl-substituted 2,2,2-trifluoroethanols and their conversion into 2,2,2-trifluoroethanethiols using Lawesson’s reagent

Mlostoń, Grzegorz; Hamera-Fałdyga, Róża; Celeda, Małgorzata; Gebicki, K.; Heimgartner, Heinz

doi:10.1016/j.jfluchem.2016.06.017

Cited by 6 publications

(6 citation statements)

References 24 publications

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“…Even though perfluorinated alcohols are of great interest in material chemistry, synthesizing trifluoromethyl thiols is reported scarcely. The tertiary trifluoromethyl thiols were synthesized via aromatic thioketones and Ruppert-Prakash reagent, but a mixture of products was formed, leading to the low yield of thiols [65].…”

Section: Synthesis Of Biologically Active Thiols and Thioethersmentioning

confidence: 99%

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A Focused Review of Synthetic Applications of Lawesson’s Reagent in Organic Synthesis

Khatoon

Abdulmalek

2021

Molecules

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Lawesson’s reagent (LR) is a well-known classic example of a compound with unique construction and unusual chemical behavior, with a wide range of applications in synthetic organic chemistry. Its main functions were rounded for the thionation of various carbonyl groups in the early days, with exemplary results. However, the role of Lawesson’s reagent in synthesis has changed drastically, and now its use can help the chemistry community to understand innovative ideas. These include constructing biologically valuable heterocycles, coupling reactions, and the thionation of natural compounds. The ease of availability and the convenient usage of LR as a thionating agent made us compile a review on the new diverse applications on some common functional groups, such as ketones, esters, amides, alcohols, and carboxylic acids, with biological applications. Since the applications of LR are now diverse, we have also included some new classes of heterocycles such as thiazepines, phosphine sulfides, thiophenes, and organothiophosphorus compounds. Thionation of some biologically essential steroids and terpenoids has also been compiled. This review discusses the recent insights into and synthetic applications of this famous reagent from 2009 to January 2021.

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Section: Synthesis Of Biologically Active Thiols and Thioethersmentioning

confidence: 99%

“…The unsuccessful attempt to prepare trifluoromethyl thiols inspired Mloston et al [65] to examine selected alcohols with LR. The powerful thionating properties of LR are well known, as well as the conversion of alcohols to thiols.…”

Section: Synthesis Of Biologically Active Thiols and Thioethersmentioning

confidence: 99%

A Focused Review of Synthetic Applications of Lawesson’s Reagent in Organic Synthesis

Khatoon

Abdulmalek

2021

Molecules

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“…The reaction of primary alcohols and phenols does not provide the corresponding thiols but phosphonodithioic acids, which were already prepared 20 years previously through the reactions between alcohols and phosphorus pentasulfide . Alcohols bearing a phenyl ring at the alcoholic carbon atom undergo thionation more readily, although a clear competition occurs with the corresponding elimination reaction . Presumably, in many cases, such an elimination has not been reported because the target was the corresponding thiol and a detailed study of the reaction was not undertaken.…”

Section: Introductionmentioning

confidence: 99%

“…For our initial M062X/6‐31+G(d,p) study, we used 1,1‐diphenylethanol ( 3a ), which affords thiol 5a and alkene 7a under different reaction conditions (Scheme ). [10c], [11b]…”

Section: Introductionmentioning

confidence: 99%

Pivotal Neighboring‐Group Participation in Substitution versus Elimination Reactions – Computational Evidence for Ion Pairs in the Thionation of Alcohols with Lawesson's Reagent

et al. 2017

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The mechanism of the thionation of alcohols with Lawesson's reagent was explored through quantum chemical DFT methods. Evidence that carbocations are involved was found. The mechanism is completely different to that established recently for the thionation of carbonyls. The presence of a phenyl ring at the alcoholic carbon atom exerts a pivotal role in the stability of the carbocation and enables a S–π interaction, which is crucial for favoring thionation instead of undesired elimination. The influence of the solvent was also studied, and elimination is preferred in toluene, whereas substitution leading to thionation is favored in acetonitrile. A clear correlation between solvent polarity and elimination was observed. The study is in complete agreement with the different behavior observed experimentally for primary, secondary, and tertiary alcohols (bearing a phenyl ring or not), and the best conditions for minimizing undesired elimination can be predicted.

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“…is a straightforward method for their conversion into the corresponding thiols [6,7]. In some recent publications, we described the synthesis of hetaryl and ferrocenyl ketones and their conversions into the sulfur analogues, i.e.…”

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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Synthesis of ferrocenyl- and hetaryl-substituted 2,2,2-trifluoroethanols and their conversion into 2,2,2-trifluoroethanethiols using Lawesson’s reagent

Cited by 6 publications

References 24 publications

A Focused Review of Synthetic Applications of Lawesson’s Reagent in Organic Synthesis

A Focused Review of Synthetic Applications of Lawesson’s Reagent in Organic Synthesis

Pivotal Neighboring‐Group Participation in Substitution versus Elimination Reactions – Computational Evidence for Ion Pairs in the Thionation of Alcohols with Lawesson's Reagent

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

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