Carbonylations with CO₂ as the CO Source and Reactivity Modifier

Abstract

A CO surrogate: In two recent studies, CO has not only been applied as a CO source in the hydroformylation of alkenes and the carbonylative Hiyama-Denmark coupling of aryl iodides, but more interestingly it also attenuates or improves the reactivity of the reactants.

N‐Formylation of Amines with CO2 and H2 by Using NHC–Iridium Coordination Assemblies as Solid Molecular Catalysts

“…As one of the most inexpensive, renewable and abundant C1 resource, the utilization of carbon dioxide (CO 2 ) for syntheses of feedstock and value‐added chemicals has attracted intensive attentions from both laboratory and industry . Therefore, in recent years, great efforts have been devoted to explore and develop efficient catalysts for this purpose.…”

“…formamidesi ng ood to excellenty ields (75-94 %, 4a-c, 5,a nd 6). Similar as cyclic cases, acyclic symmetric and asymmetric secondarya mines were also compatible and readily converted into the desired products in moderate to excellent yields (53-93 %,[7][8][9][10][11][12][13][14]. In the case of volatile dimethylamine (for safety reason, [Me 2 NH 2 ] + ·[Me 2 NCOO] À was applied instead),am oderate yield was still presented to produce DMF (53 %, 8).…”

“…As one of the most inexpensive, renewable and abundantC 1 resource, the utilization of carbon dioxide( CO 2 )f or syntheses of feedstock and value-added chemicals has attracted intensive attentions from both laboratory and industry. [1][2][3][4][5][6][7][8][9] Therefore, in recent years, great efforts have been devoted to explorea nd develope fficient catalysts for this purpose. Among all diverse direct transformations of CO 2 ,N -formylationo fa mines with CO 2 and H 2 constitutes as traightfoward, atom-economic and sustainable approach, in which water is the only by-product.…”

“…As compiled in Ta ble 2, diverse secondary and primary amines were selected for this purpose. Cyclic amines including pyrrole,p iperidine, azepane and 1,4-piperazinew ere all well tolerated to produce [9][10][11][12][13]. In the case of primary amines, even better outcomes were presented (77-97 %, 15-23), wheneverb earing aliphatic acyclic and cyclic chains, aromatica nd heterocyclic substitutes, furtherh ighlighting the protocol efficiency.H eterocyclic substrate, such as 2-picolylamine and furan-2-ylmethanamine still delivered the corresponding products in excellent yields (77-89 %, [18][19].…”

Palladium-Catalyzed External-CO-Free Carbonylation of Aryl Bromides Using 2,4,6-Trichlorophenyl Formate

“…To solve this problem, many research groups have worked on the development of CO surrogates that generate CO in situ, and several safe and facile carbonylation reactions using CO surrogates have been reported. [11][12][13][14][15][16][17][18] Recently, we and Tsuji et al independently reported Pd-catalyzed carbonylation reactions using a liquid CO surrogate, phenyl formate. It was found to react with weak bases (e.g., NEt 3 ) at elevated temperatures to form CO and phenol, and could be employed in external-CO-free carbonylation reactions in situ.…”