73270-38-9

Upstream product

• 1733-58-0 phenacyldiphenylphosphine oxide 
• 100-39-0 benzyl bromide 
• 93-89-0 benzoic acid ethyl ester 
• 3582-84-1 (2-phenylethyl)diphenylphosphine oxide 
• 93-58-3 benzoic acid methyl ester 
• 7608-18-6 phenylethynyl diphenylphosphine oxide 
• 13146-23-1 copper(I) phenylacetylenide 
• 4559-70-0 Diphenylphosphine oxide 
• 2129-89-7 diphenyl(methyl)phosphine oxide 

Downstream Products

• 1083-30-3 dihydrochalcone 
• 3412-44-0 (1E)-1,3-diphenylpropene 
• 5209-18-7 cis-1,3-diphenylpropene 

Relevant academic research and scientific papers

An efficient preparation of β-ketophosphine oxides from alkynylphosphine oxides with benzaldehyde oxime as a hydroxide source

An effective and facile transitio-metal-free method has been developed for the synthesis of β-ketophosphine oxides from alkynylphosphine oxides with benzaldehyde oxime as a hydroxide surrogate. The current methodology provides simple access to various β-ketophosphine oxides in moderate to excellent yields with a broad substrate scope.

Copper-catalyzed tandem phosphination-decarboxylation-oxidation of alkynyl acids with H-phosphine oxides: A facile synthesis of β-ketophosphine oxides

The general method for the tandem phosphination-decarboxylation-oxidation of alkynyl acids under aerobic conditions has been developed. In the presence of CuSO4·5H2O and TBHP, the reactions provide a novel access to β-ketophosphine oxides in good to excellent yields. This transformation allows the direct formation of a P-C bond and the construction of a keto group in one reaction.

Diphenylphosphinoyl-mediated synthesis of ketones

α-Diphenylphosphinoyl ketones are selectively and sequentially alkylated at the α-position. Double lithiation and selective alkylation occurs at the less stabilised γ-position. Dephosphinoylation of the alkylation products gives ketones. Mono-alkylation is selective, highly crystalline intermediates are formed and a one-pot strategy is possible. The method is ideally suited for the preparation of acid-sensitive ketones. The Royal Society of Chemistry 2006.

The synthesis of alkenes via epi-phosphonium species: 1. An anti-Wittig elimination

Anti-1,2-phosphinyl alcohols 11 and their corresponding syn-isomers upon treatment with phosphorus trichloride and triethylamine give E and Z alkenes respectively, by an anti elimination. This is in marked contrast to the syn Horner-Wittig elimination of the corresponding 1,2-phosphinoyl alcohols. The 1,2-phosphinyl alcohols 11 were prepared by the reduction of 1,2-phosphinoyl alcohols with cerium(III) chloride/lithium aluminium hydride. The anti elimination is explained by the formation of a transient epi-phosphonium species. An unexpected E-selective Horner-Wittig elimination during the cerium(III) chloride/lithium aluminium hydride reduction of a 1,2-phosphinoyl alcohol in which the diphenylphosphinoyl group is adjacent to an aryl group is described. This led to the synthesis of the antimitotic agent E- combretastatin A-4. An alternative synthesis of the 1,2-phosphinyl alcohols from the corresponding phosphine-borane complex is also described.

Opposite stereochemical effects exerted by CeCl3 and TiCl4 on the Lewis acid mediated reduction of α-alkyl-β-ketophosphine oxides with metallic hydrides: A highly stereoselective protocol for the synthesis of syn and anti α-alkyl-β-hydroxyphosphine oxides

A general, highly efficient methodology for obtaining both syn and anti α-hydroxyphosphine oxides by reduction of the corresponding α-ketophosphine oxides is described. The nature of the Lewis acid was found to be pivotal in determining the outcome of these reactions. Strongly chelating TiCl4 led to the anti isomer in high diastereoisomeric excess in noncoordinating solvents (CH2Cl2) at -78°C with BH3/py as reducing agent, while nonchelating CeCl3 gave a high excess of the syn isomer in coordinating solvents (THF) at the same temperature with LiBH4 as reducing agent. In the latter case, CeCl3 is essential in achieving high yields and stereoselectivity, since it allows the reaction to be performed at low temperatures. Otherwise, higher temperatures (0 °C) are required, which lower both yields and selectivities. Moreover, each step of the protocol for the synthesis of stereodefined disubstituted olefins from alkylphosphine oxides (Warren's modification of the Homer procedure) has been optimized, and the optimized procedure has been applied to the synthesis of muscalure, the pheromone of the domestic fly.

TiCl4 mediated LiBH4 reduction of β-ketophosphine oxides: A high stereoselective route to the synthesis of anti-β-hydroxyphosphine oxides

The reduction of an α-alkyl-β-ketophosphine oxide with LiBH4 in presence of a strong chelating agent, such as TiCl4, gives the corresponding β-hydroxyphosphine oxide in high yields and with high anti-diastereoselectivity independently from the size of both the α- and β-alkyl chains.

Reactions of Anions from α-Diphenylphosphinoyl Ketones with Electrophiles

Anions from α-Ph2P(O)-ketones do not give Horner-Wittig reactions but do react with alkyl halides, including α-halogenocarbonyl compounds, and Michael acceptors.The products may be stereoselectively reduced.