N²‐Selective Autocatalytic Ditriazolylation Reactions of Cyclopropenones and Tropone with N¹‐Sulfonyl‐1,2,3‐triazoles

Abstract

N2‐Selective autocatalytic ditriazolylation reactions of cyclopropenones and tropone with N1‐sulfonyl‐1,2,3‐triazoles are reported for the first time. In contrast to previous methods for preparing N2‐substituted bis(1,2,3‐triazolyl) compounds, the present reaction achieved ditriazolylation in one step under simple and user‐friendly conditions with a wide substrate scope. A plausible mechanism has been proposed relying on preliminary mechanistic investigations.magnified image

Synthesis of Substituted Tropones and Advancement for the Construction of Structurally Significant Skeletons

“…In 2017, Jian Hao, Yin Wei, Min Shi, and co‐researchers reported the N 2 ‐selective autocatalytic ditriazolylation reactions involving tropone, cyclopropane, and N 1 ‐sulfonyl‐1,2,3‐triazoles (Scheme 26) (Table 4). [93] The conditions for the ditriazolylation reaction between tropone 34 and N 1 ‐sulfonyl‐1,2,3‐triazole 154 were optimized. After studying various solvents, it was found that 4 equivalents of 154 a in DCE (1,2‐dichloroethane) provided the desired 1,4‐ditriazolylation product 155 a at 80 °C with a good yield of 85 % in 2.5 h. The optimized condition for the reaction of 2,3‐diphenylcyclopropenone with 154 a involves 4.0 equivalents of 154 a , 1.0 equivalent of 2,3‐diphenylcyclopropenonein DCE and it produced an excellent yield of the corresponding product (97 %) at 80 °C in 2.5 h. Surveying the substrate for the reaction of 34 and 154 under optimized conditions, it was observed that 154 having para‐ or meta ‐substituted aromatic ring afforded the corresponding product with a yield of 33–80 %.…”

Heterocycles from cyclopropenones

“…When 4phenyl-1-tosyl-1H-1,2,3-triazole (80) reacted with of 2,3-diphenylcyclopropenone (1b) in DCE for 2.5 h, 2,2 0 -(2,3-diphenylcycloprop-2-ene-1,1-diyl)bis(4-phenyl-2H-1,2,3-triazole) (81) was obtained in 97% yield (Scheme 49). 96 Hassan et al reported that a series of thiadiazoles 83a-p were obtained in 69-84% yield, via a catalyst-free reaction between 1b and alkenylidene hydrazine carbothioamides 82a-p in dry ethanol. 97 The reaction mechanism was explained by the attack of the azomethine (CH]N) nitrogen atom of compound 82 to the carbonyl group of 1b.…”

“…When 4-phenyl-1-tosyl-1 H -1,2,3-triazole ( 80 ) reacted with of 2,3-diphenylcyclopropenone ( 1b ) in DCE for 2.5 h, 2,2′-(2,3-diphenylcycloprop-2-ene-1,1-diyl)bis(4-phenyl-2 H -1,2,3-triazole) ( 81 ) was obtained in 97% yield (Scheme 49). 96…”

Progress in Synthesis of N-Sulfonyl-1,2,3-triazole and Its Application in Organic Synthesis

“…Synthesis of N-dialkylaminomethyl-2H-1,2,3triazoles 施敏等 [46] [48] . 该反应所需的最少反应时间仅为 30 min, 最高 收率可达 99%.…”