Mono and double Mizoroki–Heck reaction of aryl halides with dialkyl vinylphosphonates using a reusable palladium catalyst under aqueous medium

Abstract

2-Aryl or 2,2-diaryl vinylphosphonates can be selectively obtained by using aryl halides or dialkylvinylphosphonate as the limiting reagent.

Advances in deep eutectic solvents and water: applications in metal- and biocatalyzed processes, in the synthesis of APIs, and other biologically active compounds

“…The greenness of the reaction was showcased by an effective reuse of the residual aqueous solution for both the reported couplings (Scheme 8b). 58…”

“…Different DESs have been screened to overcome the problem of the poor solubility of steroids in aqueous solutions. The addition of 6% (v/v) of ChCl/urea (1 : 2) boosted the dehydrogenation of cortisone acetate into prednisone acetate by Arthrobacter simplex, 117 whereas the mixture ChCl/Gly (1 : 2) was found to improve the 15α-hydroxylation of D-ethylgonendione (57) to the corresponding 15α-hydroxy-Dethylgonendione (58), mediated by Penicillium raistrickii. This is a key biotransformation in the industrial synthesis of Gestodene steroids (Scheme 21).…”

In Situ Generated Palladium on Aluminum Phosphate as Catalytic System for the Preparation of β,β-Diarylated Olefins by Matsuda–Heck Reaction

“…In a precedent publication one of us described the utilization vinyl phosphonic esters in the Matsuda–Heck reaction . Synthetic protocols toward the synthesis of bis-arylated vinylphosphonates are scarce in literature, and all procedures have moderate yields and a limited range of accessible substrates. − Quite recently Tsai et al reported the first synthesis of bis-arylated vinylphosphonates via Heck reaction using aryl iodides as electrophiles . When considering that the phosphonic ester moiety represents a functional group that is isosteric to ester functionalities in medicinal chemistry, the synthesis of bis-arylated vinylphosphonates should be an auspicious target.…”

“…18−23 Quite recently Tsai et al reported the first synthesis of bis-arylated vinylphosphonates via Heck reaction using aryl iodides as electrophiles. 24 When considering that the phosphonic ester moiety represents a functional group that is isosteric to ester functionalities in medicinal chemistry, the synthesis of bisarylated vinylphosphonates should be an auspicious target. The synthetic applicability of our new catalytic procedure using the Matsuda−Heck reaction could be extended to the facile synthesis of these compounds for the first time (Table 3).…”

“…Similar to our prior findings utilizing methyl acrylate, only a monosubstituted Heck product could be obtained in the case of a nitro substituted diazonium salt (entry 5, Table 3). Compared to the protocol published quite recently by Tsai et al using aryl iodides 24 in the Mizoroki−Heck reaction, this procedure distinguishes itself by lower reaction temperatures, lower palladium loadings, and shorter reaction times. Furthermore, the presented method is characterized by its simplicity, the broader scope of substrates, and the higher yields compared to the classical procedures described in literature.…”