80403-10-7

Upstream product

• 3607-17-8 3-bromopropyltriphenylphosphonium bromide 
• 2129-89-7 diphenyl(methyl)phosphine oxide 
• 51860-45-8 3-hydroxypropyltriphenylphosphonium bromide 
• 603-35-0 triphenylphosphine 
• 889-57-6 3-(diphenylphosphinoyl)-1-propanol 
• 98-88-4 benzoyl chloride 
• 30698-18-1 bromure de benzoyloxy-3 propyltriphenylphosphonium 

Downstream Products

• 1151979-18-8 4,5-dihydro-3-diphenylphosphinoyl-2-phenyl-4-trimethylsilyl-furan 
• 89625-17-2 erythro-2-Diphenylphosphinoyl-1-phenylbutane-1,4-diol 
• 89625-14-9 2-(diphenyl-phosphinoyl)-4-hydroxy-1-phenyl-butan-1-one 
• 122552-34-5 3-benzoyl-3-diphenylphosphinoylpropyl benzoate 
• 122552-38-9 4-diphenylphosphinoxy-1-phenylbutan-1-one 
• 89625-17-2 threo-2-diphenylphosphinoyl-1-phenylbutane-1,4-diol 

Relevant academic research and scientific papers

Asymmetric synthesis of trans-disubstituted cyclopropanes using phosphine oxides and phosphine boranes

The stereocontrolled synthesis of trans-disubstituted cyclopropylketones has been achieved from β-alkyl, γ-benzoyl phosphine oxides via a three-step cascade reaction incorporating an acyl transfer, phosphinoyl transfer and cyclisation to form the cyclopropane. Using Evans' chiral oxazolidinone auxiliary and by masking the phosphine oxide moiety as a phosphine borane we have extended the method to the synthesis of enantiomerically-enriched trans-disubstituted cyclopropyl ketones.

The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing that phosphine sulfides readily undergo both phosphinoyl transfer and cyclopropane ring closure just like their phosphine oxide counterparts. The obtained data show that phosphine oxides are easily lithiated and undergo phosphoryl transfer much more readily and faster than phosphine sulfides and phosphine boranes. The observations suggest that it would be possible to perform reactions involving phosphine oxides in the presence of phosphine boranes or phosphine sulfides, potentially allowing regioselective alkylation of phosphine oxides in the presence of phosphine boranes or phosphine sulfides.

ACYL TRANSFER REACTIONS WITH PHOSPHINE OXIDES: SYNTHESIS OF E-HOMOALLYLIC ALCOHOLS, CYCLOPROPYL KETONES, AND γ-HYDROXY KETONES

Esters of 3-hydroxypropylphosphine oxides rearrange in base by O to C acyl (RCO) transfer to give the hydroxy ketones (8). threo-Selective reduction of (8) leads to pure E-homoallylic alcohols whilst C to O acyl )Ph2PO) transfer leads to γ-hydroxy ketones with nucleophilic aqueous base or cyclopropyl ketones with BuOKt - HOBut.

SYNTHESIS OF E-HOMOALLYLIC ALCOHOLS, γ-HYDROXYKETONES, AND CYCLOPROPYL KETONES FROM 3-DIPHENYLPHOSPHINOYL (Ph2PO) PROPANOLS BY ACYL TRANSFER

Carboxyl transfer (O*C) on 3-Ph2PO propyl esters (9) gives an intermediate (10) from which the Ph2PO group may be removed by the Horner-Witting reaction or by Ph2PO transfer (C*O) to give the title compounds.

SYNTHESIS OF SINGLE ISOMERS (E OR Z) OF UNSATURATED ALCOHOLS BY THE HORNER-WITTIG REACTION

Single isomers (E or Z) of homoallylic and higher alcohols can be synthesised from ω-hydroxyalkyldiphenylphosphine oxides and aldehydes, or from alkyldiphenylphosphine oxides and lactones