63103-81-1

Upstream product

• 42009-12-1 1-phenyl-2-(diphenylphosphinoyl)propan-1-one 
• 100-52-7 benzaldehyde 
• 1733-57-9 ethydiphenylphosphine oxide 
• 63103-81-1 (1RS,2SR)-1-phenyl-2-(diphenylphosphinoyl)propan-1-ol 
• 39895-79-9 triphenyl-ethyl-phosphonium cation 
• 119554-77-7 C₂₇H₂₆NOP 
• 93-89-0 benzoic acid ethyl ester 
• 17985-99-8 ethyldiphenylphosphine N-phenylimide 

Downstream Products

• 766-90-5 cis-1-phenyl-1-propylene 
• 62556-17-6 (E)-diphenyl(1-phenylprop-1-en-2-yl)phosphine oxide 
• 42009-12-1 1-phenyl-2-(diphenylphosphinoyl)propan-1-one 
• 873-66-5 1-propenylbenzene 
• 63103-81-1 (1RS,2RS)-1-phenyl-2-(diphenylphosphinoyl)propan-1-ol 
• 637-50-3 1-phenylpropene 
• 1733-57-9 ethydiphenylphosphine oxide 

Relevant academic research and scientific papers

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.

Functionalized Phosphine Imides. Diastereoselective Synthesis of β-Hydroxyphosphorylated Derivatives

The diastereoselective synthesis, of 2-hydroxyalkyldiphenylphosphine phenylimides 2 and oxides 3 by reaction of α-metallated phosphine imides with aldehydes is described.When dimethylformamide or dimethyl disulfide were used as electrophiles, functionaliz

The Stereocontrolled Horner-Wittig Reaction: Synthesis of Disubstituted Alkenes

Addition of the lithium derivatives of phosphine oxides Ph2P(O)CH2R1 to aldehydes gives erythro adducts (11) with good stereoselectivity.Reduction of α-diphenylphosphinoyl ketones (12) gives threo adducts (11) with even better stereoselectivity.Purification by flash chromatography and/or crystallisation followed by elimination of Ph2PO2 gives pure Z- or E-alkenes with high material conversion.Explanations are offered for the stereoselectivities, conditions defined for full stereochemical control, and guidelines suggested for approaches to a given alkene.

Diastereoselectivity in the Horner-Wittig Reaction: X-Ray Crystal Structure of 2-(1RS,2SR)-Diphenylphosphinoyl-1-phenylpropan-1-ol

Ethyldiphenylphosphine oxide reacts with butyl-lithium and benzaldehyde to give the title compound which eliminates diphenylphosphinate ion in base to give Z-1-phenylpropene.The elimination is stereospecific and syn.The (1RS,2RS) isomer, prepared by sodium borohydride reduction of the corresponding ketone, gives E-1-phenylpropene.

CIS-OLEFINS FROM THE HORNER-WITTIG REACTION; ORIGIN AND OPTIMISATION OF STEREOCHEMISTRY

Conditions are described to produce high yields of erythro Horner-Wittig intermediates: stereospecific elimination gives cis-alkenes.

TRANS ALKENES BY STEREOSELECTIVE REDUCTION OF α-Ph2PO KETONES: E-ISOSAFFROLE, E-ANETHOLE, AND FENICULIN

Conditions are described for the stereoselective reduction of α-Ph2PO ketones and stereospecific elimination from the resulting threo Horner-Witting intermediates to give pure E-alkenes such as the title compounds.

Stereochemically Pure E- and Z-Alkenes by the Wittig-Horner Reaction

Pure Z-alkenes are obtained stereospecifically from erythro-alcohols (3) formed on addition of Ph2PO-stabilised anions to aldehydes; acylation of the same anions, reduction of the α-Ph2P(O) ketones (5) to the threo-alcohol (6), and elimination gives pure E-alkenes.