3541-56-8Relevant academic research and scientific papers
Revisiting the phospha-Wittig-Horner reaction
Arkhypchuk, Anna I.,Santoni, Marie-Pierre,Ott, Sascha
experimental part, p. 1118 - 1126 (2012/04/10)
P,P-Dichlorophosphines 2a-c (RPCl2, R = Ph (a), t-Bu (b), 2,4,6-Me3Ph (c)) and P,P-dibromophosphines 4d,e (RPBr2, R = (i-Pr)3SiC≡C (d) and H2C=CH (e)) react with triethylphosphite under Michaelis-Arbuzov conditions to give phosphinodiphosphonates 3a-e in quantitative yields. After complexation to W(CO)5 and treatment with CH3ONa, phospha-Wittig-Horner reagents 9a,b are obtained on a multigram scale in good overall yield. Phospha-Wittig-Horner reagents with unsaturated substituents at IIIP (10d,e) can be prepared in analogous procedures; however, they prevail in an unusual ylide form that allows conjugation between the lone pair and the acetylene and vinyl π-systems, respectively. Phosphinophosphonate 9a has been characterized by X-ray crystallography and is shown to react smoothly with acetone within minutes. The resulting W(CO)5-coordinated phosphaalkene is shown to dimerize to a 1,2-diphosphitane or to undergo a 1,3-proton shift depending on the reaction conditions. In addition, a one-pot synthetic sequence starting from W(CO)5-coordinated phosphinodiphosphonates 5d,e has been developed to engage compounds with vinyl and acetylene substituents in phospha-Wittig-Horner reactions.
ZUR KENNTNIS DER ORGANOPHOSPHORVERBINDUNGEN XXIII. UEBER ALKENYLSUBSTITUIERTE AMINO-BZW. HALOGENPHOSPHANE UND VERSUCHE ZUM INTRAMOLEKULAREN PHOSPHINIDENABFANG
Diemert, Klaus,Kottwitz, Beatrix,Kuchen, Wilhelm
, p. 307 - 320 (2007/10/02)
Aminophosphanes RP(NEt2)2 and R2P(NEt2), obtained from alkenyl Grignard compounds RMgX (R = -CH=CH2, -CH2CH=CH2, o-(CH2=CH)C6H4-, o-(CH2=CHCH2)C6H4-) and aminochlorophosphanes, reacted smoothly with hydrogen halide to give alkenylhalogenophosphanes RPX2 and R2PX (X = Cl, Br).Properties and reactions of some of these compounds, e.g. with S8, H2O2, H2O and LiAlH4 are reported.On reaction of RPX2 with magnesium only alkenylcyclophosphanes (RP)n were obtained while heterocycles as possible products of an intramolecular reaction of intermediately formed phosphinidenes were not observed.
