Synthesis of Novel α-Amino-N-substituted Thioacetimidates

Synthesis of α-amino amides via α-amino imidoylbenzotriazoles

“…Reactions of the N-(a-aminoalkyl)benzotriazoles 10a-k with isonitriles 11a-c in the presence of boron trifluoride etherate in THF at 25 o C gave a-amino imidoylbenzotriazoles 12a-q in excellent isolated yields (Scheme 2, Table I). 30 The structures of compounds 12a-q 30 were supported by their 1 H and 13 C-NMR spectra and by elemental analyses (See Experimental section).…”

“…23,24 Benzotriazole is a versatile synthetic auxiliary for organic synthesis 25,26 and imidoylbenzotriazoles are synthetically useful stable alternatives to the corresponding imidoyl chlorides. [27][28][29][30][31][32] a-Amino-1-imidoylbenzotriazoles 12 were previously prepared by the reaction of 1-(1-aminoalkyl)benzotriazoles 10 with isonitriles 11 and utilized in the synthesis of novel a-amino thioimidates 13 (Scheme 2). 30 We now report the application of a-amino imidoylbenzotriazoles 12e-j,l,o-q for the preparation of a-amino amides 14a-j (Scheme 3).…”

“…[27][28][29][30][31][32] a-Amino-1-imidoylbenzotriazoles 12 were previously prepared by the reaction of 1-(1-aminoalkyl)benzotriazoles 10 with isonitriles 11 and utilized in the synthesis of novel a-amino thioimidates 13 (Scheme 2). 30 We now report the application of a-amino imidoylbenzotriazoles 12e-j,l,o-q for the preparation of a-amino amides 14a-j (Scheme 3).…”

Asmic Isocyanide [3 + 2] Cascade to Dihydrooxazoles and Dihydroimidazoles

“…Thioimidates, such as 6a , exhibit an electrophilicity greater than imidates without the inherent instability of the more reactive imidoyl chlorides . In keeping with this reactivity trend, exposure of 6a to 2-naphthalenethiol (NapSH) selectively reacted with the thioimidate to afford 18a whereas exposure of 6a to aniline selectively gave the amidine 19a (eq ).…”

First Practical Synthesis of Formamidine Ureas and Derivatives.

“…15 -Electrophilic activation by N-halobenzotriazoles (via intermediate imidoyl benzotriazoles). 16 -Uncatalyzed attack by secondary amines on electron-deficient isonitriles, such as a-cyanoa-carboxylate or a-cyano-a-phosphonate varieties. 17,18 -Oxidative activation by (and incorporation of) chloramines T, 19,20 sulfenyl chlorides, 21 or elemental selenium.…”