115880-87-0

Upstream product

• 683-08-9 Diethyl methylphosphonate 
• 78-84-2 isobutyraldehyde 
• 1499-21-4 Diphenylphosphinic chloride 
• 62199-59-1 (3-methyl-1-butynyl)diphenylphosphine 
• 2129-89-7 diphenyl(methyl)phosphine oxide 
• 244266-71-5 (2-hydroxy-3-methylbutyl)diphenylphosphine oxide 

Relevant academic research and scientific papers

Rhodium-catalyzed reaction of 1-alkynylphosphines with water yielding (E')-l-alkenylphosphine oxides

Treatment of 1-alkynylphosphines with a rhodium catalyst in l,4-dioxane/H20 at reflux provides (E)-1 -alkenyl-phosphine oxides in good yields with perfect stereoselectivity. The reaction proceeds as follows. Oxidative addition of 1 -alkynylphosphine to rhodium followed by hydrolysis yields the corresponding terminal alkyne and diphenylphos-phine oxide. Rhodium-catalyzed hydrophosphinylation of the terminal alkyne then proceeds to afford (E)-1 -alkenylphosphine oxide.

Palladium-catalyzed cascade reaction of α,β-unsaturated sulfones with aryl iodides

Unlike traditionally used acyclic 1,2-disubstituted alkenes, the reaction of α,β-unsaturated phenyl sulfones with aryl iodides under Heck reaction conditions (Pd(OAc)2 as catalyst, Ag2-CO3 as base in DMF at 120°C) takes place mainly by a cascade process, involving one unit of the alkene and three units of the aryl iodide, to afford a substituted 9-phenylsulfonyl-9,10-dihydrophenanthrene, The dominant formation of this 3:1 coupling product, instead of the Heck trisubstituted olefin, shows that aromatic C-H activation processes can compete with the usually fast syn β-hydrogen elimination step in the Heck arylation of an acyclic olefin. The structural scope of this palladium-catalyzed cascade arylation of α,β-unsaturated sulfones has proved to be wide with regard to substitution at the β-position (alkyl, aryl, or alkenyl substitution), substitution at the sulfone unit (alkyl or phenyl sulfones), and configuration at the C=C bond (trans or cis). Moreover, although less favored than in the case of the arylation of α,β-unsaturated sulfones, similarly substituted 9,10-dihydrophenanthrenes have also been obtained in the case of α,β-unsaturated phosphine oxides and α,β-unsaturated phosphonate esters. A Pd0-pdII-pdIV mechanistic pathway involving the successive formation of highly electrophilic σ-alkylpalladium intermediates and palladacycles is proposed for this multi-component arylation.

Diastereoselective nucleophilic additions to vinyl phosphine oxides

Some hydrogen, carbon, silicon, sulfur, nitrogen and oxygen nucleophiles react diastereoselectively with γ-oxygenated chiral vinyl phosphine oxides to give β-substituted phosphine oxides. Lithium N-benzyl-α-methylbenzylamide adds to prochiral vinyl phosphine oxides in the presence of trimethylsilyl chloride to provide, after protodesilylation, β-amino phosphine oxides as single diastereoisomers.

Asymmetric addition of Davies's chiral lithium amide to prochiral vinyl phosphine oxides

Lithium N-benzyl-α-methylbenzylamide adds to prochiral vinyl phosphine oxides in the presence of trimethylsilyl chloride to provide, after protodesilylation, β-amino phosphine oxides as single diastereoisomers. A mechanism which explains the role of trimethylsilyl chloride is proposed.

PREPARATION OF DIPHENYLVINYLPHOSPHINE OXIDES BY THE PCP PROCESS. CHOICE OF THE LEAVING CROUP.

Carbanionic conversion of alkyl into vinylphosphonates is extended to the preparation of diphenylvinylphosphine oxides.Obtention of pure products in optimized yields is closely related to the choice of the phosphate leaving group.