tert-Butyl nitrite promoted transamidation of secondary amides under metal and catalyst free conditions

Abstract

Transamidation of secondary amides with various amines is demonstrated using tert-butyl nitrite. The reaction proceeds through the N-nitrosamide intermediate and provides the desired products in excellent yields.

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

“…To overcome this, Kandasamy group reported a metal‐free protocol for the trans ‐amidation of secondary amide ( 43 ) using TBN at ambient temperature. The developed methodology is catalyst and additives free, which is the main advantage of the reaction (Scheme ) …”

“…The developed methodology is catalyst and additives free, which is the main advantage of the reaction (Scheme 31). [61] Similar to N-nitroso compounds, C-nitroso compounds are also extensively present in many bioactive compounds. Introductiono fn itroso functionality in imidazo[1,2-a]pyridine has gained much attention, as they exhibit excellent biological activities including antitumor,a ntibacterial, anti-inflammatory,antiviral, etc.…”

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

“…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). a Reaction conditions: glucal 1a (52 mg, 0.125 mmol) and the catalyst (0.012 mmol, 10 mol%) were added to a solution of the aryldiazonium compound generated in situ from aniline 2a (30 mg, 0.25 mmol, 2.0 equiv) and tert-butyl nitrite (0.029 mL, 0.25 mmol, 2.0 equiv) in the appropriate solvent (4 mL).…”

Direct Synthesis of N,N-Disubstituted Formamides by Oxidation of Imines Using an HFIP/UHP System

“…The reaction was then stirred at 45 ºC in a sand bath for 15 hours, until the reaction was judged to be completed by GC-MS. After this time, the reaction mixture was filtered over silica/celite plug and then the solvent was evaporated and the crude material was directly purified by flash chromatography or preparative TLC using hexane/ethyl acetate mixtures. 18 36.6,31.9,29.7,29.2,27.8,25.7,25.5,25.4,24.9,24.4,24.2 ppm;MS (EI): m/z 195 (M + , 15%), 179 (20), 178 (34), 152 (15), 138 (12), 136 (25), 114 (100), 113 (11), 98 (47), 97 (12), 96 (20), 83 (16), 82 (15), 81 (21), 69 (18), 67 (24), 56 (13), 55 (52), 54 (20); HRMS (GC/MS-EI/Q-TOF):…”