NDLI: Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride)

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Molecular springs, muscles, rheostats, and precessing gyroscopes: from review to preview

Self-assembled multivalent carbohydrate ligands

Recent approaches towards the asymmetric synthesis of α,α-disubstituted α-amino acids

An unusual stereoselectivity in the anomeric substitution with carbamates promoted by HNTf₂

Efficient ruthenium and copper cocatalzyed five-component coupling to form dipropargyl amines under mild conditions in water

Lewis acid catalyzed ring-opening reactions of methylenecyclopropanes with diphenylphosphine oxide in the presence of sulfur or selenium

Chemo-enzymatic synthesis and biological evaluation of photolabile nicotinic acid adenine dinuclotide phosphate (NAADP⁺)

Structural basis for cyclophellitol inhibition of a β-glucosidase

Selective intercalation of six ligand molecules in a self-assembled triple helix

Synthesis and properties of nicked dumbbell and dumbbell DNA conjugates having stilbenedicarboxamide linkers

Metal-driven ligand assembly in the synthesis of cyclodextrin [2] and [3]rotaxanes

Synthesis and pharmacology of glutamate receptor ligands: new isothiazole analogues of ibotenic acid

Ring expansion reactions of 4-amino-1,1-dioxo-[1,2,3,5]-thiatriazoles

Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride)

The aminolysis of N-aroyl β-lactams occurs by a concerted mechanism

Synthesis and evaluation of caged Garcinia xanthones

On the enantioselective olefin epoxidation by doubly bridged biphenyl azepine derivatives – mixed tropos/atropos chiral biaryls

Investigation of a general base mechanism for ester hydrolysis in C–C hydrolase enzymes of the α/β-hydrolase superfamily: a novel mechanism for the serine catalytic triad

Chemoenzymatic synthesis of trans-dihydrodiol derivatives of monosubstituted benzenes from the corresponding cis-dihydrodiol isomers

Structural and theoretical investigation of 2-iminoimidazolines – carbene analogues of iminophosphoranes

Synthetic ansamycins prepared by a ring-expanding Claisen rearrangement. Synthesis and biological evaluation of ring and conformational analogues of the Hsp90 molecular chaperone inhibitor geldanamycin

Density functional study of the conformations and intramolecular proton transfer in thiohydroxamic acids

Tetraurea calix[4]arenes with sulfur functions: synthesis, dimerization to capsules, and self-assembly on gold

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Organic & Biomolecular Chemistry Vol -4

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Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride)

Content Provider	Royal Society of Chemistry (RSC)
Author	Page, Michael I. Laws, Andrew P. Jansa, Petr Fettes, Kevin Hanusek, Jiří Russell, Mark A. Atherton, John H.
Copyright Year	2007
Abstract	Contrary to a previous report, the sulfurisation of phosphorus(III) derivatives by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products. The reaction of xanthane hydride with triphenyl phosphine or trimethyl phosphite yields triphenyl phosphine sulfide or trimethyl thiophosphate, respectively, and thiocarbamoyl isothiocyanate which has been trapped with nucleophiles. The reaction pathway involves initial nucleophilic attack of the phosphorus at sulfur next to the thiocarbonyl group of xanthane hydride followed by decomposition of the phosphonium intermediate formed to products. The Hammett ρ-values for the sulfurisation of substituted triphenyl phosphines and triphenyl phosphites in acetonitrile are ∼ −1.0. The entropies of activation are very negative (−114 ± 15 J mol−1 K−1) with little dependence on solvent which is consistent with a bimolecular association step leading to the transition state. The negative values of ΔS≠ and ρ values indicate that the rate limiting step of the sulfurisation reaction is formation of the phosphonium ion intermediate which has an early transition state with little covalent bond formation. The site of nucleophilic attack has been also confirmed using computational calculations.
Starting Page	478
Ending Page	484
Page Count	7
File Format	HTM / HTML PDF
ISSN	14770520
Volume Number	5
Issue Number	3
Journal	Organic & Biomolecular Chemistry
DOI	10.1039/b616298c
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Thioether Thiophosphate Phosphorus Isothiocyanate Ion Triphenylphosphine Phosphonium Carbon disulfide Thioketone Acetonitrile Trimethyl phosphite Covalent bond Hammett equation Hydride Correlation and dependence Solvent Organosulfur compounds
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Physical and Theoretical Chemistry

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Highly efficient synthesis of 2-mercaptobenzothiazole derivatives in water: metal sulfide–disulfide dynamic interchange reaction

Photochemical reactions of 4-thiouridine disulfide and 4-benzylthiouridine—the involvement of the 4-pyrimidinylthiyl radical

Correlation between the Rate Order and the Number of Molecules in the Reaction of Trimethyl Phosphite with Water in Acetonitrile Solvent

Electron-rich heteroaroylphosphonates and their reaction with trimethyl phosphite

Density functional study of the conformations and intramolecular proton transfer in thiohydroxamic acids

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Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride)

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