Completely stereoselective PC bond formation via base-induced [1,3]- and [1,2]-intramolecular rearrangements of aryl phosphinates, phosphinoamidates and related compounds: generation of P-chiral β-hydroxy, β-mercapto- and α-amino tertiary phosphine oxides and phosphine sulfides

✍ Scribed by Tin-Lok Au-Yeung; Ka-Yee Chan; Richard K Haynes; Ian D Williams; Lam Lung Yeung

• Publisher: Elsevier Science
• Year: 2001
• Tongue: French
• Weight: 114 KB
• Volume: 42
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)01952-3

✦ Synopsis

Upon treatment with LDA or alkyllithium, enantiomers of P-chiral phosphinates, phosphinothioates, phosphinoamidates, thionophosphinates, thionophosphinothioates and thionophosphinoamidates undergo clean [1,3]-and [1,2]-rearrangements with complete stereoselectivity, with retention of configuration at phosphorus, to provide functionalised tertiary phosphine oxides and phosphine sulfides; the [1,2]-rearrangements of the phosphinoamidates are previously unrecorded.