Iodine-catalyzed ammoxidation of methyl arenes

Abstract

The development of organic transformation using cheap and readily available substrates under mild conditions will be pivotal for green and sustainable synthetic organic chemistry. Concerning our continued interest in the cyanation reaction, a metal-free direct ammoxidation of readily available methyl arenes leading to nitriles was established under mild conditions. A series of aryl methanes especially heteroaryl methanes (30 examples) were applicable in moderate to good yields with good functionality tolerance.

Photoinduced Copper(I)‐Catalyzed Cyanation of Aromatic Halides at Room Temperature

“…Another common method, the Sandmeyer reaction involving the diazotization of anilines suffers from an explosion hazard. In industry, ammoxidation with toluene derivatives under high‐pressure O 2 and toxic NH 3 at highly elevated temperatures (300–550 °C) is commonly used but restricted to a narrow scope due to such harsh conditions …”

Quinoline‐Flanked Diketopyrrolopyrrole Copolymers Breaking through Electron Mobility over 6 cm2 V−1 s−1 in Flexible Thin Film Devices

“…The synthetic routes for PQDPP‐T and PQDPP‐2FT are depicted in Figure b. The important intermediate 6‐bromoquinoline‐2‐carbonitrile 2 was synthesized via a one‐step iodine‐catalyzed ammoxidation of 6‐bromo‐2‐methylquinoline 1 reported by Cheng . However, the yield of 2 decreased obviously, when this procedure was carried out in gram scale.…”

Metal‐Free Cross‐Dehydrogenative Coupling (CDC): Molecular Iodine as a Versatile Catalyst/Reagent for CDC Reactions

“…[62] Oxidation of the CÀHb ond adjacent to the heteroatom in 268 by I 2 The direct conversiono fm ethylarenes into aryl nitriles under aerobic oxidation conditions has been reported (Scheme 51). [63] Methylarenes bearinge lectron-richs ubstituents provide the cyanation products in better yields than those with electron-poors ubstituents. Also, heteroaromatic substratesa re well tolerated and give the corresponding products in good yields.…”