75128-90-4

Upstream product

• 124-13-0 Octanal 
• 219617-17-1 methyl (diphenoxyphosphoryl)acetate 
• 21204-67-1 methyl (triphenylphosphoranylidene)acetate 
• 111-87-5 octanol 
• 302571-63-7 methyl 2-chloro-3-hydroxydecanoate 
• 191018-96-9 methyl 2-[bis(2,4-difluorophenoxy)phosphoryl]acetate 
• 191018-97-0 methyl bis(4-fluorophenyl)phosphonoacetate 
• 176538-82-2 methyl bis-1,1,1-trichloroethyl phosphonoacetate 
• 88738-78-7 bis-(2,2,2-trifluoroethyl)(methoxycarbonylmethyl)phosphonate 
• 5927-18-4 trimethyl phosphonoacetate 
• 35060-79-8 Nonadien-1,4-carbonsaeure-1-methylester 

Relevant academic research and scientific papers

Expansion of substrate scope for nitroxyl radical/copper-catalyzed aerobic oxidation of primary alcohols: A guideline for catalyst selection

Four distinctive sets of optimum nitroxyl radical/copper salt/additive catalyst combinations have been identified for accommodating the aerobic oxidation of various types of primary alcohols to their corresponding aldehydes. Interestingly, less nucleophilic catalysts exhibited higher catalytic activities for the oxidation of particular primary allylic and propargylic alcohols to give α,β-unsaturated aldehydes that function as competent Michael acceptors. The optimum conditions identified herein were successful in the oxidation of various types of primary alcohols, including unprotected amino alcohols and divalent-sulfur-containing alcohols in good-to-high yields. Moreover, N-protected alaninol, an inefficient substrate in the nitroxyl radical/ copper-catalyzed aerobic oxidation, was oxidized in good yield. On the basis of the optimization results, a guideline for catalyst selection has been established.

Wittig reactions in water media employing stabilized ylides with aldehydes. Synthesis of α,β-unsaturated esters from mixing aldehydes, α-bromoesters, and Ph3P in aqueous NaHCO3

(Chemical Equation Presented) 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 α-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, α-bromoesters, and aldehydes in sodium bicarbonate solution (at 20°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.

Synthesis of (E)-a,β-unsaturated esters and amides with total selectivity using samarium diiodide

β-elimination of α-halo-β-hydroxyesters 1 was achieved by using samarium diiodide as a metalating reagent, and afforded di- and trisubstituted (E)-α,βunsaturated esters 2 with total steroselectivity. This method has also been extended to the corresponding disubstituted (E)-α,β-unsaturated amides.

Highly cis-selective Horner-Wadsworth-Emmons (HWE) reaction of methyl bis(2,4-difluorophenyl) phosphonoacetate

Of the previously reported Homer-Wadsworth-Emmons (HWE) reaction, the olefination of methyl bis(2,4-difluorophenyl)phosphonoacetate (1a) with various aldehydes gave unsaturated esters in the highest cis-selectivity.

Electronic effects on the Z(cis)-selectivity of Horner-Wadsworth-Emmons olefination reaction

Various phosphorates have been synthesized to study the Horner-Wadsworth-Emmons olefination reaction. The phosphoryl stabilised carbanion resulting from phosphonates, carrying electron withdrawing groups attached to phosphorus atom, has been reacted with a variety of aldehydes at - 78°C leading to Z(cis) selective olefination.

DIRECT SYNTHESIS OF Z-UNSATURATED ESTERS. A USEFUL MODIFICATION OF THE HORNER-EMMONS OLEFINATION.

New phosphonoester reagents and reaction conditions are described which yield Z-alpha,beta-unsaturated esters stereoselectively and in high yield from aliphatic and aromatic aldehydes.