Diphenylvinylphosphine oxide

Compared with acyclic analogues, cyclic hydrogen phosphorodithioates are highly reactive towards diphenylvinylphosphine oxide and diethyl [a-(ethoxycarbo-nyl)styryl]phosphonate, the six-membered-ring acids reacting more quickly than the five-membered-ring acids or the acyclic compounds. On the other hand, the nucleophilic reactivity of anions of the acids towards benzyl halides is less for the cyclic systems than for the acyclic ones. ... 

Diphenylvinylphosphine oxide (14) and p-styryldiphenylphosphine (164) were obtained at or below room temperature in tetrahydrofuran with a small excess of Grignard reagent ... 

Boron trifluoride catalyses the 1,3-phosphotropic rearrangement of the a-phosphorylated imine (65) to give (66).35 This reaction takes place at room temperature, whereas the uncatalysed reaction requires heating to 150-2000C. High yields of the addition products (67) have been obtained from the reaction of carbon-centred radicals with diphenylvinylphosphine oxide.36 Radical addition to the chiral phosphine oxides (68) using Barton s method provides diastereomeric ratios of up to 9 1 in the case of (69). 

Free-radical-catalysed additions have also been reported, and provide a genuine alternative to the more familiar base-catalysed addition routes. Thus the secondary diphosphine (28) readily adds to diphenylvinylphosphine in the presence of AIBN to give (29).25 Similarly, addition of di(pentafluorophenyl)phosphine to diphenylvinylphosphine affords26 the diphosphine (30). Sequential addition of silanes and secondary phosphines to terminal aco-dienes under the influence of u.v. light affords the silylalkylphosphines (31), which may be anchored via silicon to the surface of inorganic oxides and used as polymeric catalysts.27... 

HRu3(CO)s( Ph2PCH=CH2)( Ph2PC2H2) obtained by oxidative addition of diphenylvinylphosphine to Ru3(CO)i2 on TLC plates. 

---