Potassium tert‐Butoxide‐Mediated Amine Acyl Exchange Reaction of N,N‐Disubstituted Formamides with Aromatic Carbonyl Derivatives via Sequential CN Bond Cleavage/Formation: an Approach to Aromatic Amides

Abstract

An ovelp otassium tert-butoxide-mediated amine acyl exchangeo fN,N-disubstituted formamides with aromatic carbonylderivatives in asequential C À Nb ondc leavage/formation process leading to aromatic amides is described. This methodology tolerates awide range of aromaticcarbonyl compounds, including aromatica ldehydes,a cylc hlorides, unactivated esters, anda cid anhydrides.T he usage of inexpensive and readily available reagents,b road sub-strate scope,a nd the simple,m ild (50 8 8C) and transition metal-free conditions make this protocol very practical. In addition,aplausible reactionm echanism is proposed on the basis of experimental observations.

Cobalt(II)‐Catalyzed N‐Acylation of Amines through a Transamidation Reaction

“…[3,4‐Dihydroisoquinolin‐2(1 H )‐yl](phenyl)methanone (2zd): Purified by TLC to give 2zd (32 %) as a yellow oil. 1 H NMR (400 MHz, CDCl 3 ): δ = 7.44 (s, 5 H), 7.22–7.17 (m, 4 H), 4.90 (major rotamer, s, 1.14 H), 4.59 (minor rotamer, s, 0.86 H), 4.00 (minor rotamer, s, 0.69 H), 3.64 (major rotamer, s, 1.10 H), 2.97 (minor rotamer, s, 0.95 H), 2.88 (major rotamer, s, 1.24 H) ppm.…”

Metal- and solvent-free synthesis of amides using substitute formamides as an amino source under mild conditions

“…These results indicated that the decomposition of formamide derivative and the corresponding decomposition product amine might be played an important role in this amide synthesis procedure. Based on these control experiments and previous studies 13,29 , a possible mechanism was proposed (Fig. 5).…”

Metal‐Free, Regioselective, Dehydrogenative Cross‐Coupling between Formamides/Aldehydes and Coumarins by C–H Functionalization

“…The reactions proceeded smoothly and delivered the desired products regioselectively functionalized at C‐3 in moderate‐to‐good yields with aliphatic as well as alicyclic formamides ( 3a – 3e , Table ). However, no product was observed with diphenylformamide ( 3f , Table ), probably for steric reasons …”