An effective new access to ethyl 2-[(alkylamino)(cyano)methyl] acrylates: first synthesis of ethyl 3-cyano-2-(hydroxymethyl) acrylate

Efficient synthesis of allylamines from a novel (E)-2,3-difunctionalized allyl bromide

“…17,18 Continuing with our efforts directed toward the development of new methodologies for the synthesis of functionalized brominated derivatives, [19][20][21][22][23][24] we describe in this paper an efficient alternative for the preparation of a new family of allyl bromide (E)-4 and vinyl bromide (E)-5 from tetraethyl prop-2-ene-1,2-diyldiphosphonate 2 (Scheme 1) with complete stereoselectivity in favour of the E configuration starting from inexpensive reagents. Allyl bromide (E)-4 has been separated and then transformed in a one-step synthesis, to a new family of tetraethyl 1-(alkylamino)prop-2-ene-1,2-diyldiphosphonates 6.…”

A Mild Synthesis of New Aryl Vinyl Ethers and Diethyl 1-[(Alkyl)(cyano)methyl]vinylphosphonates via the Substitution of a 2,3-Difunctional Allyl Bromide

“…It has resulted in a wide variety of applications in the preparation of several natural [1–4] as well as biologically active compounds [5–8]. Moreover, the utility of these versatile allyl brominated intermediates 1 [9–18] comes from their reaction with different nucleophilic species and additionally their ability to act as excellent Michael acceptors. Because of its importance, it is still of interest to develop novel approaches for the efficient generation of functionalized allyl bromide 1 .…”

A practical synthesis of diethyl 1-[(alkylamino)(cyano)methyl]vinylphosphonates

“…1,2 Indeed, allyl bromides constitute the core structures of numerous natural products [3][4][5] and biologically active compounds. [5][6][7][8] Considering the increased importance of bromomethylated compounds [9][10][11][12][13][14] and in connection with our research projects [15][16][17][18] on the utility of allyl bromides, we report here a novel synthetic method of diethyl For both compounds (E)-3 and (E)-4, the preferred configuration being E as confirmed by two-dimensional NMR (NOESY). Indeed, there is no correlation between the ethylenic proton (6.09 ppm) and those of methyl group (1.29 ppm) for the allyl nitrile 3, then the vinylic proton (6.26 ppm) and those of CH 2 Br (4.18 ppm) in the case of the allyl bromide (E)-4.…”

“…It should be noted that these compounds might be effective precursors in organic synthesis 22 , including biologically active products such as Streptogramin antibiotics, 23 alkaloids 24 and antifungal chemotherapeutic agents, 25 and in several naturally occurring compounds. [26][27][28][29][30][31][32] Because of the importance of functionalized allylamines 17,18,[33][34][35][36] and their applications, we report herein a simple and economical method for their synthesis from the reaction coupling of allyl bromide (E)-4 with various primary amines in methanol at 0 °C. As reported in our previous works, 18,33 allyl bromide (E)-4 could be considered as an allyl cation equivalent which reacts with a variety of nucleophiles including primary amines.…”

“…[26][27][28][29][30][31][32] Because of the importance of functionalized allylamines 17,18,[33][34][35][36] and their applications, we report herein a simple and economical method for their synthesis from the reaction coupling of allyl bromide (E)-4 with various primary amines in methanol at 0 °C. As reported in our previous works, 18,33 allyl bromide (E)-4 could be considered as an allyl cation equivalent which reacts with a variety of nucleophiles including primary amines. Thus, the regioselectivity and the abnormal (S N 2 ) substitution product can be explained by the increased electrophilicity of -carbon of (E)-4 leading to a new family of diethyl 1-[(alkylamino) (cyano)methyl]vinylphosphonates 5 a-h in moderate yields (Scheme 5, Table 1).…”