Thiophosphinic Acids: Historic Overview and Recent Advances in their Synthesis and Applications

Vassiliou, Stamatia

doi:10.2174/138527211796150642

Cited by 10 publications

(4 citation statements)

References 38 publications

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“…From the methods available for the synthesis of thiophosphonic acids [ 44 , 45 ], we selected racemic 1-adamantyl aryl- H -phosphinates ( 1 ) as starting materials for the preparation of the corresponding arylthiophosphonic acid derivatives ( 2 ). The 1-adamantyl aryl- H -phosphinates ( 1 ) were synthesized according to a literature procedure [ 24 ].…”

Section: Resultsmentioning

confidence: 99%

Enantioseparation of P-Stereogenic 1-Adamantyl Arylthiophosphonates and Their Stereospecific Transformation to 1-Adamantyl Aryl-H-phosphinates

et al. 2023

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A focused library of 1-adamantyl arylthiophosphonates was prepared in racemic form. An enantioseparation method was developed for P-stereogenic thiophosphonates using (S)-1-phenylethylamine as the resolving agent. Under optimized conditions, three out of the five arylthiophosphonates were prepared in enantiopure form (ee > 99%). The subsequent desulfurization of optically active arylthiophosphonates gave the corresponding H-phosphinates without significant erosion of enantiomeric purity (ee = 95–98%). Hence, this reaction sequence can be considered an alternative method for the preparation of 1-adamantyl aryl-H-phopshinates. The absolute configuration of the (S)-1-adamantyl phenylphosphonothioic acid was assigned using single-crystal XRD and it allowed the confirmation that the removal of the P = S group proceeds with retention of configuration. The organocatalytic applicability of (S)-1-adamantyl phenylphosphonothioic acid was also evaluated as a P-stereogenic Brønsted acid.

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Section: Resultsmentioning

confidence: 99%

Enantioseparation of P-Stereogenic 1-Adamantyl Arylthiophosphonates and Their Stereospecific Transformation to 1-Adamantyl Aryl-H-phosphinates

et al. 2023

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“…Any and all literature methods were considered toward our objective of synthesizing thiophosphorus acids. ,− Very quickly various issues were identified in some of the methods, and as a result, they were deemed unacceptable.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, our laboratory became interested in the preparation of thiophosphorus acids R 1 R 2 P(S)OH 1 , in connection with a project aimed at developing novel chiral phosphorus acids (CPAs) organocatalysts . Thiophosphorus acids have been known for a long time, and resolution to a chiral compound was described as early as 1958 .…”

Section: Introductionmentioning

confidence: 99%

Evaluation and Development of Methodologies for the Synthesis of Thiophosphinic Acids

Winters

Montchamp

2020

J. Org. Chem.

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Thiophosphorus acids R1R2P(S)OH constitute an important class of organophosphorus compounds, in which the phosphorus atom is intrinsically chiral if R1 ≠ R2. In connection with a project aimed at the preparation of chiral thiophosphorus acids, various available literature methods were considered, but few fit the requirement of odorless reagents. Herein, the results of our studies on the synthesis of thiophosphinic acids are reported. Ultimately, two major approaches were selected: (1) the Stec reaction of phosphorus amides with carbon disulfide; and (2) the one-pot synthesis of thiophosphorus acids from H-phosphinates, an organometallic nucleophile, and quenching with elemental sulfur. An application to the preparation of a potential chiral phosphorus organocatalyst is also reported.

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“…In contrast to phosphinyl dipeptide isosters, there is no scientific report concerning thiophosphinyl dipeptide isosters (TDIs). A thorough overview of the literature revealed the absence of any synthetic method providing this class of compounds. The only relevant approaches dealt with the synthesis of Cbz-GlyΨ[P(S)(OH)]CH 3 and Cbz-GlyΨ[P(S)(OH)]CH 2 OH as a potent inhibitors of bacterial ureases.…”

Section: Introductionmentioning

confidence: 99%

Mapping the Pathway toward Thiophosphinic Pseudopeptides. Synthesis of Suitably Protected PG-Phe-Ψ[P(S)(OX)CH₂]-Gly-OY Analogues as Thiophosphinyl Dipeptide Isosters (TDI), a Comparative Study for Selective Deprotection and Further Elongation

Vassiliou

Tzouma

2013

J. Org. Chem.

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In the present study, we describe in detail the first synthesis of a new class of phosphorus compounds, thiophosphinyl pseudopeptides. We prepared several fully protected thiophosphinate pseudodipeptides of the general formula PG-Phe-Ψ[P(S)(OX)CH2]-Gly-OY starting from the corresponding phosphinate pseudodipeptide using Lawesson's reagent. Selective deprotection, further elongation, and stability of these compounds were studied, and the results are disclosed. These compounds can be used as transition-state-mimicking inhibitors for several zinc metalloproteases.

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Thiophosphinic Acids: Historic Overview and Recent Advances in their Synthesis and Applications

Cited by 10 publications

References 38 publications

Enantioseparation of P-Stereogenic 1-Adamantyl Arylthiophosphonates and Their Stereospecific Transformation to 1-Adamantyl Aryl-H-phosphinates

Enantioseparation of P-Stereogenic 1-Adamantyl Arylthiophosphonates and Their Stereospecific Transformation to 1-Adamantyl Aryl-H-phosphinates

Evaluation and Development of Methodologies for the Synthesis of Thiophosphinic Acids

Mapping the Pathway toward Thiophosphinic Pseudopeptides. Synthesis of Suitably Protected PG-Phe-Ψ[P(S)(OX)CH₂]-Gly-OY Analogues as Thiophosphinyl Dipeptide Isosters (TDI), a Comparative Study for Selective Deprotection and Further Elongation

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Thiophosphinic Acids: Historic Overview and Recent Advances in their Synthesis and Applications

Cited by 10 publications

References 38 publications

Enantioseparation of P-Stereogenic 1-Adamantyl Arylthiophosphonates and Their Stereospecific Transformation to 1-Adamantyl Aryl-H-phosphinates

Enantioseparation of P-Stereogenic 1-Adamantyl Arylthiophosphonates and Their Stereospecific Transformation to 1-Adamantyl Aryl-H-phosphinates

Evaluation and Development of Methodologies for the Synthesis of Thiophosphinic Acids

Mapping the Pathway toward Thiophosphinic Pseudopeptides. Synthesis of Suitably Protected PG-Phe-Ψ[P(S)(OX)CH2]-Gly-OY Analogues as Thiophosphinyl Dipeptide Isosters (TDI), a Comparative Study for Selective Deprotection and Further Elongation

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Mapping the Pathway toward Thiophosphinic Pseudopeptides. Synthesis of Suitably Protected PG-Phe-Ψ[P(S)(OX)CH₂]-Gly-OY Analogues as Thiophosphinyl Dipeptide Isosters (TDI), a Comparative Study for Selective Deprotection and Further Elongation