| Autor: |
Andrzej Łopusiński, M. M. Kabachnik, Leszek Łuczak, Jan Michalski, M. Moriyama |
| Rok vydání: |
1981 |
| Předmět: |
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| Zdroj: |
Tetrahedron. 37:2011-2020 |
| ISSN: |
0040-4020 |
| DOI: |
10.1016/s0040-4020(01)97955-4 |
| Popis: |
Optically active t-butylphenylphosphinothiocyanidate Bu t PhP(O)SCN 3 and t-butyl-O-methyl-phosphonothiocyanidate Bu t (MeO)P(O)SCN 7 have been prepared by condensation of the corresponding sulphenyl chlorides > P(O)SCl with trimethylsilylcyanide and isomerised into optically active t-butyl-O-methyl-phos-phonoisothiocyanidates Bu t (MeO)P(O)NCS 8 . Chirality at P in and the optical purity of the chiral phosphino (phosphono) thiocyanidates and isothiocyanidates have been determined by chemical correlations. It has been demonstrated that the thiocyanate ion and amine catalysed thiocyanidate-isothiocyanidate isomerisation > P(O)SCN → > P(O)NCS occurs stereospecifically with inversion of configuration at the P center. This result can be rationalized by postulation of a phosphorane intermediate, formed by nucleophilic attack of the SCN - anion on phosphorus, in which thiocyanate and isothiocyanate groups occupy apical positions. In connection with these studies a number of novel optically active phosphorylated derivatives of carbonic acid, > P(O)NHCSNHR, > P(O)NCCl 2 , > P(O)NCO and > P(O)NHCOOBu t , have also been synthesised. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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