P-Substituted 3-phosphabicyclo [3.1.0] hexane 3-oxides from diastereoselective substitution at phosphorus

✍ Scribed by György Keglevich; Attila Kovács; László Tőke; Kálmán Újszászy; Gyula Argay; Mátyás Czugler; Alajos Kálmán

• Publisher: John Wiley and Sons
• Year: 1993
• Tongue: English
• Weight: 593 KB
• Volume: 4
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.520040405

✦ Synopsis

Preparation of P-am ino-3-phosphabicy clo [ 3.1.01hexane 3-oxides either by addition of dichlorocarbene to the double bond of l-amino-2,5-dihydro-l Hphosphole 1 -oxides or by substitution of the P-chloro derivative of the bicyclic system was accomplished. Two different diastereomers are obtained by the two approaches; their 13C NMR spectra were interpreted on the basis of the P-ethoxy isomers, whose stmctures were confirmed by X-ray analysis. The P-hydroxy adduct was also prepared, and it was found that intermolecular 0-H . . . 0 hydrogen bonding connects the molecules together in the solid phase. This effect eliminates the possibility of diastereoisomerism, as was also observed in the case of P-hydroxy tetrahydrophosphinine oxides. Thennolysis of the P-hydroxy adduct is a better way to synthesize 1hydroxy-l,2-dihydrophosphinine oxides than by hydrolysis of the phssphinic chlorides.