Totally Regio- and Stereoselective P–O-to-P–C Rearrangement in the Synthesis of Chiral P-(o-Hydroxyaryl)diazaphospholidine P-Oxides

✍ Scribed by Olivier Legrand; Jean Michel Brunel; Gérard Buono

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 323 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/(sici)1099-0690(199905)1999:5<1099::aid-ejoc1099>3.0.co;2-r

✦ Synopsis

The totally regio-and stereoselective P-O-to-P-C exception was found with naphthyl derivatives, which gave mixtures of two regioisomers. In all cases, the products rearrangement in the synthesis of various chiral P-(ohydroxyaryl)diaza-phospholidine P-oxides has been generated have been unambiguously characterized by 1 H-, 13 C-, and 31 P-NMR spectroscopy as well as by X-ray-investigated. This reaction proceeds with excellent yields ranging from 72 to 92%, total retention of configuration at diffraction analysis. the phosphorus atom, and complete regioselectivity. An quence involving an unstable metallated intermediate. The

Results and Discussion

Chiral P-(o-hydroxyaryl)diazaphospholidine P-oxides 2 may be synthesized from precursors 1 in a two-step se-Scheme 2. General procedure for the synthesis of precursors 1 [a]