Transamidation for the Synthesis of Primary Amides at Room Temperature

Abstract

Various primary amides have been synthesized using the transamidation of various tertiary amides under metal-free and mild reaction conditions. When (NH4)2CO3 reacts with a tertiary amide bearing an N-electron-withdrawing substituent, such as sulfonyl and diacyl, in DMSO at 25 °C, the desired primary amide product is formed in good yield with good funcctional group tolerance. In addition, N-tosylated lactam derivatives afforded their corresponding N-tosylamido alkyl amide products via a ring opening reaction.

Gram-Scale Preparation of Acyl Fluorides and Their Reactions with Hindered Nucleophiles

“…1 H NMR (400 MHz, CDCl 3 ):  = 7.95 (ddt, J = 7.9, 1.7, 0.5 Hz, 1 H), 7.56 (ddd, J = 8.1, 7.3, 1.7 Hz, 1 H), 7.49 (dtt, J = 8.1, 1.4, 0.6 Hz, 1 H), 7.38 (ddd, J = 7.9, 7.3, 1.4 Hz, 1 H). (19), 139 (48), 132 (46), 130 (93), 123 (34), 113 (14), 111 (42), 95 (58), 75 (59), 50 (38). HRMS (EI): m/z [M + ] calcd for C 7 H 4 OClF: 157.9935; found: 157.9940.…”

“…Benzamide (3a) 58 Yield: 89% (0.213 g, 1.77 mmol, 89%); white crystals; mp 126.7-127.2 °C (Lit. 59 127-128 °C). 60 Yield: 95% (0.296 g, 1.90 mmol); white crystals; mp 133.2-133.6 °C (Lit.…”

“…60 Yield: 95% (0.296 g, 1.90 mmol); white crystals; mp 133.2-133.6 °C (Lit. 59 134-136 °C). 1 H NMR (400 MHz, CDCl 3 ):  = 7.80 (d, J = 2.1 Hz, 1 H), 7.66 (d, J = 7.7 Hz, 1 H), 7.48 (dd, J = 8.0, 2.1 Hz, 1 H), 7.37 (t, J = 8.0, 7.6 Hz, 1 H), 6.16 (br s, 2 H).…”

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

“…Benzamide (3w): 22 White solid; purification by preparative TLC (hexane/ethyl acetate 9.0/1.0), ASSOCIATED CONTENT Supporting Information.…”

Facile Synthesis of Amides through Transamidation with Iodine under Neat Conditions

“…Gong and co-workers have also reported the transamidation reaction, using 15 mol% Cobalt (II) at 150 °C temperature. [26] Along with metal catalysts, the non-reagents catalyst has also been successfully catalyzed amidation transformations, with ammonium carbonate, [27] and related compounds acting as the most prominent example. Krishnamurthy and co-workers have reported a new amide bond formation between hydroxamic acids and amines.…”