Butylphenylphosphine oxides

Two reports have been made of the preparation of P-chiral phosphine oxides through reaction of chiral f-butylphenylphosphine oxide treated with LDA and electrophiles. The electrophiles included aldehydes,355 ketones,355 and benzylic-type halides.356 Optically active a-hydroxyphosphonate products have also been generated from aldehydes and dialkyl phosphites using an asymmetric induction approach with LiAl-BINOL.357... 

Haynes, R.K., Lam, W.W.-L., and Yeung, L.-L., Stereoselective preparation of functionalized tertiary P-chiral phosphine oxides by nucleophilic addition of lithiated tert-butylphenylphosphine oxide to carbonyl compounds, Tetrahedron Lett., 37, 4729, 1996. 

The selenide (111) has been prepared from t-butylphenylphosphine oxide and resolved via its salt with (+)-l-aminoethylbenzene. ... 

Buono developed a very effective synthesis of chiral tertiary phosphine oxide starting from oxazaphospholidines. The enantiomerically pure oxazaphospholidine (Rp)-122 was prepared from PhP(NMe2)2 and (,S)-(+)-prolinol. Subsequent treatment of 122 with a variety of acids followed by hydrolysis gave both enantiomers of tert-butylphenylphosphine oxide 4c. It was found that the acid controlled the stereochemistry of the enantiomer obtained. By using acids of high acidity or Amberlyst 15 resin, (-h)-(R)-4c was obtained with good yields and enantioselec-tivities. When acids of low acidity were used, ( )-(,S)-4c was the preferred enantiomer. For example, / -toluenesulfonic acid (PTSA) afforded (R)-4c in 88% yield and 91% ee. After a recrystaUization the optically pure compound (/ )-(-t)-4c was obtained with >99% ee (Scheme 37) [67]. 

Scheme 37 Preparation of (R)- and (S)-tert-butylphenylphosphine oxides 4c from oxazapho-spholidine (/fp)-122...

Gryshkim EV, Kolodiazhna AO, Kolodiazhnyi OI (2003) Synthesis of chiral tert-butylphenylphosphine oxide. J Russ Gen Chem 73 1823-1824... 

Leyris A, Nuel D, Giordano L, Achard M, Buono G (2005) Enantioselective synthesis of hoth enantiomers of tert-butylphenylphosphine oxide fiom (S)-prolinol. Tetrahedrrai Lett 46 8677-8680... 

Holt J, Majc AM, Schudde EP, Pietrusiewicz KM, Sieron L, Wieczorek W, Jerphagnon T, Arends IWCE, Hanefeld U, Minnaard AJ (2009) On the resolution of secondary phosphine oxides via diastereomeric complex formation the case of tert-butylphenylphosphine oxide. Synthesis 2061-2065... 

Aminophosphines. The synthesis and use of aminophosphines as ligands have been reviewed. Raeemie ehlorophosphines of the type R R PCl have been shown to react stereoselectively with chiral amines (1-phenylethylamine or aminoacid esters) in the presence of triethylamine to give the diastereomerically enriched aminophosphines (137), which were isolated as diastereomerically pure crystalhne borane complexes. This approach has also been used in the synthesis of chiral t-butylphenylphosphine oxide, via the acid hydrolysis of an intermediate chiral aminophosphine. Among other new mon-oaminophosphines prepared by treatment of primary or secondary amines with ehlorophosphines in the presence of a base are the adenine derivatives (138), the phosphinoalkylaminophosphines (139), " the aminophosphine-phosphine... 

Methylphenylpropylphosphine oxide, Z4.12 Isopropylmethylphenylphosphine oxide, Z4.7 rerr-Butylphenylphosphine oxide, Z"5.6 C10H15OPS... 

C20H28CUN2O7, Copper bis(tenuazonate) monohydrate, 43B, 1369 C2oH280 P2Zn, Zinc n-butylphenylphosphinate, 34B, 582 C20H3 3Cl03PRh, cis-Chlorodicarbonyl(tricyclohexylphosphine oxide)-rhodium(l), 40B, 942... 

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