6002-45-5Relevant academic research and scientific papers
Absolute configurations, predominant conformations, and tautomeric structures of enantiomeric tert-butylphenylphosphinothioic acid
Wang,Polavarapu,Drabowicz, Jozef,Mikolajczyk, Marian,Lyzwa, Piotr
, p. 9015 - 9019 (2001)
Vibrational absorption and circular dichroism spectra of dextrorotatory, levorotatory, and racemic mixture of tert-butylphenylphosphinothioic acid have been measured in CCl4 solutions in the 2000-900 cm-1 region. The conformations for both tautomeric structures of (S)-tert-butylphenylphosphinothioic acid are investigated using the B3LYP functional with the 6-31G* basis set. For the most stable conformation, the absorption and VCD spectra are predicted ab initio using the B3LYP functional with 6-31G*, 6-311G(2d, 2p), 6-31+G*, and 6-311G(3df, 3pd) basis sets. A different functional, B3PW91, was also used with the 6-31G* basis set. The predicted spectra are compared to the experimental spectra. The comparison indicates that (-)-tert-butylphenylphosphinothioic acid is of the (S)-configuration and exists in only one tautomeric structure and one conformation in CCl4 solution.
Evaluation and development of methodologies for the synthesis of thiophosphinic acids
Winters, Karen R.,Montchamp, Jean-Luc
, p. 14545 - 14558 (2020/12/29)
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.
Reductive cleavage of the halogen-phosphorus and sulfur-phosphorus bonds with alkali metals
Stankiewicz, Marek,Nycz, Jacek,Rachon, Janusz
, p. 330 - 339 (2007/10/03)
The reduction of thiophosphorus acid chlorides with alkali metals (Na, K) in liq. NH3/THF solution, potassium anthracenide, and potassium napththalenide was investigated. It was found that these types of phosphorus compounds easily undergo reduction to 〉P-S- anions. It was also demonstrated that 〉P-O- and 〉P-S- anions as well very efficiently undergo sulfurization with elementary sulfur in liquid ammonia to yield 〉P(O)S- and 〉P(S)S- anions, respectively.
Reaction of metallated tert-butyl(phenyl)phosphane oxide with electrophiles as a route to functionalized tertiary phosphane oxides: Alkylation reactions
Haynes, Richard K.,Au-Yeung, Tin-Lok,Chan, Wai-Kuen,Lam, Wai-Lun,Li, Zhi-Yi,Yeung, Lam-Lung,Chan, Albert S. C.,Li, Pauline,Koen, Mark,Mitchell, Craig R.,Vonwiller, Simone C.
, p. 3205 - 3216 (2007/10/03)
P-Chiral tertiary phosphane oxides have been prepared from each of the secondary phosphane oxides racemic 1, (S(p))-(-)-4 and (Rp)-(+)-tert-butylphenylphosphane oxide (5) by lithiation with LDA or nBuLi, or sodiation with sodium hydride, in THF, and then by treatment with a series of primary alkyl halides. Doubly P-chiral ditertiary bis(phosphane oxides) are also obtained from these metallated secondary phosphane oxides by treatment with electrophiles based on straight-chain, tartrate-derived, and bishalomethylarene dihalides. In general, the bis-phosphane oxides are obtained in good yields. However, when the α,ω-dihalide bears an embedded heteroatom (O or Si), yields are diminished. The enantiomeric purity of each of the products was assessed through admixture with (R(p))- and (S(p))-tert-butyl(phenyl)phosphanylthioic acids and measurement of the tert-butyl resonances in the 1H-NMR spectra. In all cases, the act of metallation of the enantiomerically pure secondary phosphane oxide followed by its alkylation is not accompanied by detectable racemization. This method for preparing P-chiral tertiary phosphane oxides is therefore more straightforward than those described previously.
Enzymes in organic chemistry 7.[1] evaluation of homochiral t-butyl(phenyl)phosphinothioic acid for the determination of enantiomeric excesses and absolute configurations of α-substituted phosphonates
Drescher, Martina,Felsinger, Susanne,Hammerschmidt, Friedrich,Kaehlig, Hanspeter,Schmidt, Susanne,Wuggenig, Frank
, p. 79 - 93 (2007/10/03)
α-Hydroxy-, α-acetoxy-, α-chloroacetoxy-, α-azido-, α-phthalimidooxy-, and α-aminooxyphosphonates are investigated by 1H and 31P NMR spectroscopy in the presence of homochiral t-butyl(phenyl)phosphinothioic acid as chiral solvating a
Chiral t-butylphenylphosphinothioic acid: A useful chiral solvating agent for direct determination of enantiomeric purity of alcohols, thiols, amines, diols, aminoalcohols and related compounds
Omelanczuk, Jan,Mikolajczyk, Marian
, p. 2687 - 2694 (2007/10/03)
Enantiomers of t-butylphenylphosphinothioic acid were found to be useful chiral solvating agents (CSAs) for 1H-NMR determination of enantiomeric excess (ee) of many classes of chiral organic compounds, such as alcohols, diols, thiols, mercaptoalcohols, amines, aminoalcohols, hydroxyacids and related compounds.
The Optically Active Phosphinodithioates. Synthesis and Conversion to the Optically Active Phosphine Sulfides
Kawashima, Takayuki,Kojima, Satoshi,Inamoto, Naoki
, p. 849 - 852 (2007/10/02)
The optically active phosphinodithioates were prepared by the reaction of the corresponding phosphinothioates with Lawesson's reagent in high chemical and optical yields, and were allowed to react with n-BuLi, followed by treatment with the electrophiles
