Umpolung reactivity of allylic phosphonates. A simple route to 3-aminoalkane- and 3-amino-1-alkenylphosphonates (phosphinates and phosphine oxides)

✍ Scribed by Xiyan Lu; Junhui Sun; Jingyang Zhu

• Book ID: 102846542
• Publisher: John Wiley and Sons
• Year: 1992
• Tongue: English
• Weight: 588 KB
• Volume: 3
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.520030517

✦ Synopsis

Dibutyl ullylphosphonate can react with palladium chloride to give the dibutyl phosphorylated m-ally1 palladium chloride complex which was found to be able to react with a nucleophile, such as sodium dimethyl malonate, to give a functionalized 1 -alkenylphosphonate. A 1 -acetoxyallylic phosphonate can be regarded as the precursor of a phosphorylated .rr-allylic palladium complex in a palladium(0) catalyzed reaction, and the latter reacts with nucleophiles to yield 3-substituted 1-alkenylphosphonates. The reaction is regioselective. Using this methodology, 3-aminoalkane-und 3-arninoalkenylphosphonates were synthesized from 1 -acetoxyallylic phosphonates regioselectivelv.

Dedicated to Prof. Yao-Zeng Huang on the occasion of his

'To whom correspondence should be addressed. eightieth birthday.