Synthesis and structure of dialkyl ( Z )-3-amino-2-cyano-4-diazopent-2-enedioates
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RIGINAL PAPER
Synthesis and structure of dialkyl (Z)‑3‑amino‑2‑cyano‑4‑diazopent‑2‑enedioates Issa Yavari1 · Ramin Mohsenzadeh1 · Jasmine Kayanian1 Received: 8 July 2020 / Accepted: 10 November 2020 / Published online: 22 November 2020 © Springer-Verlag GmbH Austria, part of Springer Nature 2020
Abstract Diazo-transfer reaction of tosyl azide and alkyl 2-cyanoacetates in the presence of pyridine at 0 °C gives the corresponding alkyl 2-cyano-2-diazoacetates. This material readily undergoes nucleophilic attack by pyridinium 1-cyano-2-alkoxy2-oxoethan-1-ide to form dialkyl (Z)-3-amino-2-cyano-4-diazopent-2-enedioates. The X-ray structure of a typical product is reported, as well as DFT computational studies that illuminate the structural features of these stable diazo compounds. Graphic abstract
Keywords Diazo compound · Tosyl azide · Diazo transfer · Cyanodiazoacetate · Alkyl cyanoacetate
Introduction Diazo-containing compounds are versatile reagents in organic synthesis [1–5]. The first aliphatic diazo compound, ethyl diazoacetate, was synthesized in the nineteenth century by Curtius [6] and diethyl 2-diazopentanedioate was synthesized by Chiles and Noyes [7]. A major route for the synthesis of diazo compounds involves the base-assisted reaction of an active methylene group with a diazo-transfer reagent such as p-toluenesulfonyl azide [8]. The diazo groups are extensively used as metal carbene precursors, and enable a wide variety of unique transformations including 1,3-dipolar cycloaddition, cyclopropanation, alkylation [9–12], C–H insertion [13], phosphorus or sulfur ylide formation [14], and Pd-catalyzed cross-coupling reactions [15]. Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00706-020-02712-4) contains supplementary material, which is available to authorized users. * Issa Yavari [email protected] 1
Department of Chemistry, Tarbiat Modares University, PO Box 14115‑175, Tehran, Iran
Thus, interest in the chemistry of diazo compounds has been continuous [16–19]. Diazo group is found in natural products and amino acids that show antitumor and antimicrobial activities [20–22]. Examples of these substances include azaserine [23], kinamycin [24, 25], and members of the lomaiviticin [20] (Fig. 1). Stabilized diazo compounds in which the electrons on α-carbon are delocalized onto adjacent groups enjoy high potentials for prevalent applications in chemical biology [26]. Recently, an environmentally benign method for 1,2,3-triazole synthesis with a sulfur-based side chain has been accessed with the annulation reactions of readily available β-thiolated enaminones and tosyl hydrazine [27]. Through a Regitz diazo-transfer process, domino reactions between enaminones and tosyl azide have been developed for the synthesis of N-substituted 1,2,3-triazoles [13]. The reaction of 2-cyanothioacetamides with azides in water in the presence of alkali presents an efficient method for the synthesis of 1,2,3-thiadiazol-4-carbimidamides and 1,2,3-triazole-4-carbothioa
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