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Chemistry and stereochemistry of the interaction of the water-soluble phosphine [HO(CH2)(3)](3)P with cinnamaldehyde in aqueous media

TitleChemistry and stereochemistry of the interaction of the water-soluble phosphine [HO(CH2)(3)](3)P with cinnamaldehyde in aqueous media
Publication TypeJournal Article
Year of Publication2007
AuthorsMoiseev, DV, James, BR, Hu, TQ
JournalInorganic Chemistry
Volume46
Pagination4704-4712
Date PublishedMay
ISBN Number0020-1669
Abstract

To learn more about the bleaching action of pulps by (hydroxymethyl)phosphines, cinnamaldehyde was reacted with tris(3-hydroxypropyl)phosphine, [HO(CH2)(3)](3)P (THPP), in aqueous solution at room temperature under argon. Self-condensation of the aldehyde into two isomeric products, 2-benzyl-5-phenyl-pent-2,4-dienal and 5-phenyl-2-(phenylmethylene)-4-pentenal, is observed; this implies initial nucleophilic attack of the phosphine at the beta-carbon of the alpha,beta-unsaturated aldehyde. Reaction in D2O gives the same products in which all but the phenyl and CHO protons are replaced by deuterons. NMR studies are consistent with carbanion formation and subsequent condensation of two phosphonium-containing aldehyde moieties to generate the products with concomitant elimination of phosphine oxide. In D2O in the presence of HCl, THPP reversibly attacks the aldehyde-C atom to form the (alpha-hydroxy)phosphonium derivative [PhCHC(H)CH(OD)PR3]Cl (where R = (CH2)(3)OD), which slowly converts into the deuterated bisphosphonium salt [R3PCH(Ph)CD(H)CH(OD)PR3]Cl-2 via the deuterated monophosphonium salt [R3PCH(Ph)CD(H)CHO]Cl. The phosphonium intermediates and phosphonium products in this chemistry, although having up to three chiral carbon centers, are formed with high stereoselectivity just in enantiomeric forms. In acetone-H2O (1:1 v/v), a cross-condensation of cinnamaldehyde with acetone to give 6-phenyl-3,5-hexadien-2-one is promoted by THPP via generation of OH-.

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