Stable phosphorus ylides and heterocyclic phosphonate esters derivatives synthesised from stereoselective reactions between triphenyl phosphite and activated acetylenic esters

Abstract

One-pot synthesis of stable heterocyclic phosphorus ylides 4a-j is reported in fairly good yields by the reaction between dialkyl acetylenedicarboxylates and triphenyl phosphite in the presence of strong NH-acids such as 2benzoxazolinone, 2-indolinone and 2-mercaptobenzoxazole in aqueous media as an environmentally friendly solvent. The hydrolysis of compounds 4a-f led to stable phosphonate ester derivatives 5h-l. The configuration of compounds 5h-l (2S * ,3R * ) was determined on the basis of coupling constant predicted from the Karplus equation.

X‐ray structural analysis and theoretical studies of new phosphite‐derived ylides

“…The mechanism of this reaction is similar to those that have been previously explained for the reactions between triphenylphosphine, dialkyl acetylenedicarboxylates and N-H acids [12][13][14][15][16]. As a result, speculative proposed mechanism for the formation of these compounds is explained in Scheme 2.…”

“…Phosphorus ylides constitute an important class of reagents in synthetic organic chemistry and are readily prepared by the treatment of a phosphonium salt with a base [1][2][3]. In our previous work, triphenylphosphine and triphenylphosphite were employed as phosphorus compound for the generation of stable phosphorus ylides [4][5][6][7][8][9][10][11][12][13][14][15][16]. In continuation of our research work, triethyl phosphite, despite their higher reactivity toward moisture when compared to triaryl phosphines, was employed for the generation of a new class of stable phosphorus ylides.…”

Synthesis of Dialkyl {(aryl)[2,2-Dimethyl-4-oxo-6-(Piperidin-1-yl)-4H-[1,3]Dioxin-5-yl]Methyl}Phosphonate by Reaction of Meldrum's Acid, Aryl Aldehydes and Trialkyl Phosphites in the Presence of Piperidine

“…11 There are other recent reports on the reaction between phosphites and acetylenic esters in the presence of an acidic organic compound, all of which proceed to products through a phosphite ylide intermediate. [12][13][14] However, this intermediate has not been isolated nor characterised in any of these reports and is usually hydrolysed or rearranged to the corresponding phosphonates. In the context of our recent studies [15][16][17][18][19] on the reactivity of isopropylidene Meldrum's acid, we studied the reaction between Meldrum's acid, aryl aldehydes with trialkyl phosphites in the presence of piperidine.…”

A facile synthesis, dynamic 1H NMR and theoretical study the novel stable heterocyclic phosphorus ylides containing tetrazole

“…The synthesis of phosphorus ylides is important in organic chemistry because of their application in the synthesis of organic products, [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] and especially the synthesis of naturally occurring products with biological and pharmacological activity. [20][21][22][23][24] Phosphorus ylides are usually prepared by deprotonation of phosphonium salts, which can be prepared most often by the reaction of triphenylphosphine and an alkyl halide.…”