Direct conversion of white phosphorus to versatile phosphorus transfer reagents via oxidative onioation

Photocatalytic stannylation of white phosphorus

“…2 However, it is only very recently that it has finally become possible to successfully transform P 4 directly into a variety of useful P 1 products. 3 Moreover, and despite these extensive investigations, the number of successful examples remains extremely low, and those that do exist still suffer from substantial limitations. 4 As such, there remains a clear need to expand the range of strategies available for direct, productive P 4 activation, with new catalytic methods being particularly desirable.…”

Recent Breakthroughs in P4 Chemistry: Towards Practical, Direct Transformations into P1 Compounds

“…Whereas the latter strategy was based around the reduction of P 4 to a formal source of "P 3À " followed by reaction with electrophiles, Weigand et al have developed a formal oxidation of P 4 to give a "P 3 + " synthon, which can then undergo reaction with nucleophiles. [36] Specifically, the authors describe a strategy they term "oxidative onioation", which relies on reaction of P 4 with a suitable oxidizing Lewis acid and nitrogen-centred Lewis base. Using Ph 3 As(OTf) 2 and DMAP (4-dimethylaminopyridine) was found to result in formation of the highly electrophilic trication [(DMAP) 3 P] 3 + as a noncorrosive solid in excellent yield at multigram scale (Scheme 8a,…”

Direct Synthesis of Dialkylphosphites from White Phosphorus

“…The industrial method for the preparation of (EtO) 2 P(O)H is based on two environmentally toxic steps in which 1) P 4 is first chlorinated with dangerous molecular chlorine to generate PCl 3 ; 2) three equivalents of ethanol react with PCl 3 to give the desired product along with the releasing of one equivalent of EtCl and two equivalents of HCl [7] . However, this leads to obvious drawbacks such as toxic Cl 2 , strongly acidic conditions, hazardous and corrosive PCl 3 , and organo‐chloride waste (Scheme 1a) [8] . Furthermore, the use of molecular chlorine and PCl 3 suffers from poor selectivity and poor atom economy [9] …”

“…[7] However, this leads to obvious drawbacks such as toxic Cl 2 , strongly acidic conditions, hazardous and corrosive PCl 3 , and organo-chloride waste (Scheme 1a). [8] Furthermore, the use of molecular chlorine and PCl 3 suffers from poor selectivity and poor atom economy. [9] In order to avoid the use of Cl 2 and PCl 3 , the direct transformation of P 4 into (RO) 2 P(O)H is necessary.…”