tert-Butyl nitrite mediated nitrogen transfer reactions: synthesis of benzotriazoles and azides at room temperature

Abstract

A conversion of o-phenylenediamines into benzotriazoles was achieved at room temperature using tert-butyl nitrite. The optimized conditions are also well suited for the transformation of sulfonyl and acyl hydrazines into corresponding azides. This protocol does not require any catalyst or acidic medium. The desired products were obtained in excellent yields in a short span of time.

tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

“…To demonstrate the practical utility of this method, a one‐pot click reaction was attempted successfully. Since, the reaction proceeds in neutral medium, acid labile groups were found to be intact during triazole formation (Scheme ) …”

“…To demonstratet he practical utility of this method, ao ne-pot click reaction was attempted successfully.S ince,t he reactionp roceeds in neutral medium, acid labile groupsw ere found to be intact during triazole formation( Scheme105). [133] Oxazole is au biquitous motif in many naturalp roducts and pharmaceuticals with multiple biological activities, such as antiviral,a ntibacterial, antileukemia, antitumore tc. In this context, Song group reported ao ne-pot method for the construction of highly functionalized oxazoles (144)f rom N-propargylamides (143)u sing ag old catalyst.…”

Copper-Catalyzed Redox Coupling of Nitroarenes with Sodium Sulfinates

“…4-Bromo-N-p-tolylbenzenesulfonamide ( 3s ) [68]: Off-white solid, 63% yield (41.0 mg), 1 H-NMR (400 MHz, CDCl 3 , ppm) δ 7.59 (s, 4H), 7.08 (d, J = 7.3 Hz, 2H), 6.95 (d, J = 7.0 Hz, 2H), 6.37 (s, 1H), 2.31 (s, 3H); 13 C-NMR (100 MHz, CDCl 3 , ppm) δ 138.2, 136.1, 133.2, 132.3, 130.1, 128.8, 128.0, 122.9, 20.9; MS (EI) m / z (%) 327, 106 (100), 77.…”

Palladium-Catalyzed One-Pot Stereospecific Synthesis of 2-Deoxy Aryl C-Glycosides from Glycals and Anilines in the Presence of tert-Butyl Nitrite

“…9c,d Other advantages of TBN are its low cost and commercially availability, and the fact that it is economic and easy to store and handle. We have recently demonstrated different applications of tert-butyl nitrite in organic synthesis, including N-nitrosation of secondary amines, 11 oxidative dimerization of thioamides, 12 conversion of o-phenylenediamines into triazoles, 13 nitration of Nalkyl anilines 14 and one-pot transamidation of secondary amides. 15 In continuation of this work, we herein report the palladium-catalyzed one-pot synthesis of 2,3-deoxy 3-keto aryl C-glycosides from glycals and anilines in the presence of tert-butyl nitrite under mild conditions (Scheme 1).…”

“…NMR spectra were recorded on a Bruker Avance 500 MHz NMR spectrometer. The 1 H and 13 C NMR spectra are reported as chemical shifts () in parts per million (ppm), with TMS (0.00 ppm) or residual undeuterated CDCl 3 (7.26 ppm) (for 1 H NMR spectra) and the CDCl 3 signal at 77.0 ppm (for 13…”