title: Wittig reactions in water media employing stabilized ylides with aldehydes. Synthesis of alpha,beta-unsaturated esters from mixing aldehydes, alpha-bromoesters, and Ph3P in aqueous NaHCO3.
abstract: Water is demonstrated to be an effective medium for the Wittig reaction over a wide range of stabilized ylides and aldehydes. Despite sometimes poor solubility of the reactants, good chemical yields normally ranging from 80 to 98% and high E-selectivities (up to 99%) are achieved, and the rate of the reactions in water is unexpectedly accelerated. The efficiency of water as a medium in the Wittig reaction is compared to conventional organic solvents ranging from carbon tetrachloride to methanol. The aqueous Wittig reaction works best when large hydrophobic entities are present, such as aromatic, heterocyclic aromatic carboxaldehydes, and long-chain aliphatic aldehydes with triphenylphosphoranes. The E/Z-isomeric ratio of the Wittig products appears dependent on the electron-accepting/donating capacity and the location of the substituents present in the aromatic ring. The effect of additives, such as benzoic acid, LiCl, and sodium dodecyl sulfate (SDS), on the Wittig reaction has been explored. The Wittig reaction can also be conducted in the presence of acidic entities, such as phenols and carboxylic acids. In addition, large alpha-substituents in the aliphatic aldehydes do not jeopardize the reaction. It is also demonstrated that hydrates of aldehydes can be used directly in the aqueous Wittig reaction as substrates. The scope of the aqueous Wittig reaction is extended to 24 examples of one-pot mixtures of Ph3P, alpha-bromoesters, and aldehydes in sodium bicarbonate solution (at 20 degrees C for 40 min to 3 h) to provide Wittig products of up to 99% yield and up to 98% E-selectivity. Since water is inexpensive, extremely easy to handle, and represents no environmental concerns, it should be considered a possible medium for new organic reactions.
authors.affiliation: Department of Chemistry and Biochemistry, San Diego State University, San Diego, California 92182-1030, USA.
authors.forename: Amer
authors.initials: A
authors.lastname: El-Batta
authors.forename: Changchun
authors.initials: C
authors.lastname: Jiang
authors.forename: Wen
authors.initials: W
authors.lastname: Zhao
authors.forename: Robert
authors.initials: R
authors.lastname: Anness
authors.forename: Andrew L
authors.initials: AL
authors.lastname: Cooksy
authors.forename: Mikael
authors.initials: M
authors.lastname: Bergdahl
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D001966:Bromine / Q000737:chemistry*; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010755:Organophosphates / Q000737:chemistry*; D017693:Sodium Bicarbonate / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D004952:Esters; D010755:Organophosphates; D014867:Water; D017693:Sodium Bicarbonate; D001966:Bromine; C005445:triphenyl phosphate