Synthesis and Reactions of Stabilized Phosphorus Ylides

Abstract

Stabilized phosphorus ylides, versatile intermediates in synthetic organic chemistry can be prepared by the novel reaction of dialkyl acetylenedicarboxylates (DAAD), triphenylphosphine (TPP) and acids such as phenols, imides, amides, enols, oximes and alcohols. The reaction involves an intermediate formed by the 1:1 conjugate addition reaction of the TPP to DAAD and concomitant protonation of the intermediate by an acid leads to vinyltriphenylphosphonium salts. The salts are unstable intermediates and converted to stabilized phosphorus ylides via Michael addition reaction. The stabilized phosphorus ylides are able to take part in the normal intramolecular Wittig reactions but they are not generally able to participate in the normal intermolecular Wittig reactions. The intermolecular Wittig reactions of the ylides are observed only with highly electron-poor carbonyl groups such as indane-1,2,3-trione. The ylides are converted to electron-poor alkenes via elimination of TPP in solvent-free conditions. Almost all of the final products are valuable families of compounds. †Dedicated to Professor Issa Yavari on the occasion of his 59th birthday.

Molecular Structure, NMR, FMO, MEP and NBO Analysis of ethyl-(Z)-3-phenyl-2-(5-phenyl-2H-1,2,3,4-tetraazol-2-yl)-2-propenoate Based on HF and DFT Calculations

“…In recent years, there has been an increasing interest in the applications of acetylenic esters in multicomponent synthesis, especially for preparing stabilized phosphorus ylides [13][14][15][16]. Recently, we have established a one-pot method for the synthesis of organophosphorus compounds [17][18][19].…”

Synthesis of stabilized phosphorus ylides from electron-poor alcohols and their applications in the preparation of 2,5-dihydrofuran derivatives

“…Phosphorus ylides are important reagents in synthetic organic chemistry [1][2][3][4][5][6], especially in the synthesis of naturally occurring products, compounds with biological and pharmacological activity [6]. The development of the modern chemistry of natural and physiologically active compounds would have been impossible without the phosphorus ylides [1][2][3][4][5][6].…”

“…The development of the modern chemistry of natural and physiologically active compounds would have been impossible without the phosphorus ylides [1][2][3][4][5][6]. They have found use in a wide variety of reactions of interest to synthetic chemists [1][2][3][4][5][6].…”

“…The development of the modern chemistry of natural and physiologically active compounds would have been impossible without the phosphorus ylides [1][2][3][4][5][6]. They have found use in a wide variety of reactions of interest to synthetic chemists [1][2][3][4][5][6]. These compounds have attained great significance as widely used reagents for linking synthetic building blocks with the formation of carbon-carbon double bonds, and this has aroused much interest in the study of the synthesis, structure and properties of P-ylides and their derivatives [1][2][3][4][5][6].…”

“…They have found use in a wide variety of reactions of interest to synthetic chemists [1][2][3][4][5][6]. These compounds have attained great significance as widely used reagents for linking synthetic building blocks with the formation of carbon-carbon double bonds, and this has aroused much interest in the study of the synthesis, structure and properties of P-ylides and their derivatives [1][2][3][4][5][6]. Several methods have been developed for preparation of phosphorus ylides [1].…”