The reaction of Alkyl Isocyanides and Dialkylacetylene Dicarboxylates with Phthalic Anhydride Derivatives: A Novel Synthesis of γ-spiroiminolactones

Abstract

The addition of alkyl isocyanides to dialkyl acetylenedicarboxylates in the presence of phthalic anhydride derivatives leading to highly functionalised γ-spiroiminolactones is reported.

Four-component Reaction between Aryl Aldehydes, Ethyl Cyanoacetate and Dimethyl Acetylenedicarboxylate in the Presence of Cyclohexyl Isocyanide

“…The 1 H NMR spectrum of compound 5a was very simple and exhibited two sharp signals at 3.79 and 3.81 ppm for methoxycarbonyl groups, and one NH group (δ = 8. On the basis of the well established chemistry of isocyanides [6][7][8]18 it is reasonable to assume that intermediate 7 In conclusion, we report here the four-component reaction between aryl aldehydes, ethyl cyanoacetate and dimethyl acetylenedicarboxylate with cyclohexyl isocyanide as a simple and efficient route for the synthesis of functionalised cyclopentadiene derivatives. The advantages of the reported method are that it is inexpensive with easily available starting materials, it has simple and neutral reaction conditions, gives high yields, is a single-product reaction and is a simple work-up process.…”

“…Isocyanides react easily with electron-deficient acetylenic diesters such as dimethyl acetylenedicarboxylate (DMAD) to produce a reactive zwitterionic intermediate which can be trapped by an electrophile. Recently, a wide variety of electrophiles have been applied to trap isocyanide-DMAD intermediates, among them are carbon electrophiles such as aldehydes, imines, quinonoids, 10 1,2diketones, 11 1,2,3-tricarbonyl compounds, 12 isocyanates, 13 and hydrogen electrophiles such as pyrrole, 14 amides, 15 hydroxycoumarin, 16 phenols, 17 phthalic anhydride, 18 and isatoic anhydride. 19 Treatment of the isocyanide-DMAD zwitterion with aromatic carboxylic acids has been reported to produce unsaturated amides.…”

Four-Component Reaction of Isocyanides, Acetylenic Esters, and Carboxylic Acids for the Synthesis of Functionalised 2,5-diaminofurans

“…Isocyanides react easily with electron-deficient acetylene diesters such as dimethyl acetylenedicarboxylate (DMAD) to produce a reactive zwitterionic intermediate (Scheme 1), which can be trapped by an electrophile. In recent years, a wide variety of electrophiles have been applied to trap isocyanide-DMAD intermediate, among them are carbon electrophiles such as aldehydes, imines, quinonids, 11 1,2-diketones, 12 1,2,3-tricarbonyl compounds, 13 isocyanates, 14 and hydrogen electrophiles such as pyrrole, 15 amides, 16 hydroxy coumarine, 17 phenoles, 18 phthalic anhydride, 19 and isatoic anhydride. 20 Treatment of isocyanide-DMAD zwitterion with aromatic carboxylic acids has been reported to produce unsaturated amides.…”

Reaction between Isocyanides, Dialkyl Acetylenedicarboxylates and 2-Hydroxy-1-aryl-2-(arylamino)ethanones: One-Pot Synthesis of Highly Functionalized 2-Aminofurans

“…Addition of isocyanides to acetylene diesters is well known to produce a reactive zwitterionic intermediate, which further reacts with electrophiles to afford a wide variety of carbo-and heterocycles. A wide variety of electrophiles has been applied to trap isocyanide-dimethyl acetylenedicarboxylate (DMAD) intermediate; among them are carbon electrophiles such as aldehydes, 7,8 quinones, 7 1,2-diketones, 9 1,2,3-tricarbonyl compounds, 10 imines, 11 isocyanates, 12 and hydrogen electrophiles such as pyrrole, 13 amides, 14 4-hydroxycoumarine, 15 phenols, 16 phthalic anhydride, 17 and isatoic anhydride. 18 This class of reactions has also been used for the synthesis of 2-aminofuran derivatives.…”