Phosphonodifluoromethyl and Phosphonothiodifluoromethyl Radicals. Generation and Addition onto Alkenes and Alkynes.

Abstract

Organo-phosphorus compounds S 0080 Phosphonodifluoromethyl and Phosphonothiodifluoromethyl Radicals. Generation and Addition onto Alkenes and Alkynes. -Treatment of the selenides (I) and (VII) with AIBN results in formation of the title radicals. They smoothly react with alkenes and terminal alkynes to afford difluorinated phosphonates or phosphonothioates. These compounds are of synthetic and biological interest. -(PIGNARD, S.; LOPIN, C.; GOUHIER, G.; PIETTRE*, S. R.; J. Org. Chem. 71 (2006) 1, 31-37; Lab. Fonct. Azotees Oxygenees Complexes, Inst. Rech. Chim. Org. Fine, Univ. Rouen, F-76821 Mont-Saint-Aignan, Fr.; Eng.) -Jannicke 22-178

The α,α-Difluorinated Phosphonate L-pSer-Analogue: An Accessible Chemical Tool for Studying Kinase- Dependent Signal Transduction

“…This has spurred a great effort in methodology development in this area (Benayoud et al, 1996; Blackburn et al, 1985a; Blackburn et al, 1994; Blades et al, 1997; Caplan et al, 2000; Cockerill et al, 2000; Diab et al, 2008; Gautier et al, 2004; Herpin et al, 1996; Hikishima et al, 2006; Lopin et al, 2003; Murano et al, 2005; Nair and Burton, 1997; Ozouf et al, 2004; Pajkert et al, 2008; Pfund et al, 2005; Pignard et al, 2006; Roeschenthaler et al, 2006; Xu et al, 2005; Yokomatsu et al, 2003). The phosphate mimics program in this laboratory was initiated around the goal of establishing methods to access fluorinated phosphonate analogues of sugar phosphates (Berkowitz et al, 2001; Berkowitz et al, 2000a; Berkowitz et al, 1993; Shen et al, 1994), and continues in this direction, with a particular interest, of late, in bivalent sugar phosphonates as ligands for the mannose 6-phosphate-insulin-like growth factor II receptor (M6P/IGF2R) (Berkowitz et al, 2004; Fei et al, 2008).…”

“…Related transformations have been developed in the thiono series by Piettre and colleagues, more recently (Lequeux et al, 2001; Pignard et al, 2006). These latter reactions do not require transition metal catalysis, and are routinely run under radical chain conditions.…”