ALLYLDIPHENYLPHOSPHINE OXIDE

Uses

Reactant for:

• Preparaton of a-substituted alkylsilanes via regio- and chemoselective copper-catalyzed silylzincation and electrophilic substitution from terminal alkenes, and prepn. of α-substituted alcohols via Fleming-Tamao oxidation of alkylsilanes
• Olefin isomerization with Grubbs′ catalysts occluded in a hydrophobic matrix of polydimethylsiloxane (PDMS)
• C9-substituted trans-hydrindene via diastereotopic group-selective intramolecular Diels-Alder reaction
• Isomerization of allyl group-containing compounds to propenyl group-containing compounds in the presence of a Grubbs second-generation Ru catalyst
• Ruthenium-catalyzed olefin cross-metathesis of vinyl and allyl phosphine oxides to give alkenyl phosphine oxides and bis-phosphine oxides

Synthesis

The synthesis method of Allyldiphenylphosphine Oxide: (1) rearrangement of allyl diphenylphosphinite and (2) Arbuzov reaction of alkyl diphenylphosphinite with Allyl Bromide. Other new methods have also been developed. Structurally related analogs prepared include 2- methylallyldiphenylphosphine oxide, 2-phenylallyldiphenylphosphine oxide, 1- methoxyallyldiphenylphosphine oxide, crotyldiphenylphosphine oxide, and 1-substituted allylic diphenylphosphine oxide[1].

Synthesis

Purification: recrystallization from ether/hexane, benzene/petroleum ether, cyclohexane, or benzene[2].

References

1. (a) Ukai, J.; Ikeda, Y.; Ikeda, N.; Yamamoto, H. TL 1983, 24, 4029. (b) Ikeda, Y.; Ukai, J.; Ikeda, N.; Yamamoto, H.  T 1987, 43, 723. (c) Burke, S. D.; Armistead, D. M.; Shankaran, K. TL 1986, 27, 6295.
2. Berlin, K. D.; Calvert, J. F. Proc. Okla. Acad. Sci. 1966, 46, 78