✦ LIBER ✦
Reaction of trialkyl phosphites with phosphonodithioformates: Access to substituted methylene bis-phosphonates via stabilized ylids.
✍ Scribed by Andrew Bulpin; Serge Masson; Aboubacary Sene
- Publisher
- Elsevier Science
- Year
- 1990
- Tongue
- French
- Weight
- 294 KB
- Volume
- 31
- Category
- Article
- ISSN
- 0040-4039
No coin nor oath required. For personal study only.
✦ Synopsis
The addition of 2 equivalents of trialhylphosphite to phosphonodithioformates leads to stabilized phosphonium yliak. The reaction of these yliak with hydrochloric acid, methyl iodide, benzyl-, allyl-andpropargyl-bromide is studied : C-Protonation or S-alkylation which occurs with an Arbuzov-type dealkylation gives access to substituted methylene bis-phosphonates or to stabilized sulphonium yliak
Apart from the well known desulphurisation and coupling reactions of derivatives of 1,3-dithiole-2-thiones leading to tetrathiafulvalene derivatives (constituents of organic conductors)* and the Corey-Winter olefin synthesis from cyclic thionocarbonates2, the reactions of trialkylphosphites with thiocarbonyl compounds are not commonly used in organic synthesis.
A few studies have shown that the regioselectivity of the initial thiophilic or carbophilic addition of the phosphite and the evolution of the assumed 1,3-dipolar intermediates depend on the nature of the substituents on