Novel synthesis of primary arylamides from aryl methyl ketone oxidations using iodine in aqueous ammonia

Abstract

Primary arylamides were obtained when several aryl methyl ketones were treated with iodine in aqueous ammonia at room temperature in goods yields.Arilamidas primárias foram obtidas em bons rendimentos quando diversas arilmetilcetonas foram tratadas com iodo em amônia aquosa a temperatura ambiente.

Metal-Free Synthesis of N-(Pyridine-2-yl)amides from Ketones via Selective Oxidative Cleavage of C(O)–C(Alkyl) Bond in Water

“…Direct synthesis of esters through highly selective C­(O)–C­(alkyl) bond cleavage has been reported by Jiao’s group . However, strategies for the construction of amides from ketones via C–C bond cleavage encountered many limitations: (1) unique resources of amines (most of the reported methods constructed primary amides from aqueous ammonia; (2) using excess volatile heavy atoms (a common pathway to synthesize amides via C–C bond cleavage requires excess iodine, with iodoform as the extra side product (Scheme a)); , (3) using toxic and reactive agents (some methodologies use strong nucleophilic NaN 3 as the N donor to form primary amides (Scheme b)); , (4) using metals (the Kaliappan group reported the synthesis of N -heterocyclic amides from methyl ketones using 20% Cu-catalyzed biomimetic oxidation (Scheme c)) …”

Splitting Methyl Ketones into Two Parts: Synthesis of 4(3H)-Quinazolinones via Consecutive Cyclization/Ring-Opening Reaction

“…Methyl ketones are among the most common and readily available materials applied in organic synthesis . In particular, the direct transformation of methyl ketones into valuable building blocks via cleaving the C­(CO)–C­(sp 3 ) bond has become a fascinating topic in academia and industry. − Accordingly, elegant examples of the iodide-mediated functionalization of methyl ketones via cleaving the C­(CO)–C­(sp 3 ) bond have been developed . However, these strategies remain limited to amide construction.…”

Iodine-catalyzed oxidative C–C bond cleavage for benzoic acids and benzamides from alkyl aryl ketones

“…Elimination of dimethyl sulde and formaldehyde form acyl azide V (via IV) which through known conversion affords benzamide 7. 12 In summary, we have developed a new type of iodinecatalyzed C(CO)-C(alkyl)bond cleavage of aryl/vinyl ketones/ phenylacetylenes for the synthesis of benzoic acids and benzamides via an aerobic oxidation and oxygenation process under air. This reaction has many advantages like iodine as the metal free catalyst, air as the sole terminal oxidant, cheap and readily available starting materials and a wide substrate scope.…”