Selective Palladium‐Catalyzed Aminocarbonylation of Aryl Halides with CO and Ammonia

Abstract

Wake up and smell the ammonia! A palladium‐catalyzed aminocarbonylation of aryl halides with CO and ammonia has been developed (see scheme). Primary amides are accessible, under mild reaction conditions, in moderate to excellent yields.

Palladium‐Catalyzed Carbonylative α‐Arylation for Accessing 1,3‐Diketones

“…A comparable yield was obtained when the reaction was run with the ketone in a slight excess with respect to the base (Table 1, entry 11). [13,14] An increase in the steric bulk on the phosphines resulted in the formation of the benzylic ketone 5 as the sole product, thus demonstrating the delicate balance often observed in the design of palladium catalysts (Table 1, entry 9). Finally, it is interesting to note that attempts to run these reactions under an atmosphere of Scheme 1.…”

“…The electron-poor aryl iodides displayed a slightly inferior performance, thus indicating that the CO incorporation is dependent on the electronic properties of the arylpalladium(II) intermediate formed after the oxidative addition. [14] Nevertheless, good chemoselectivity was obtained in the reactions of 3-bromo-and 3-chloroiodobenzene, 13 and 15, respectively, which allow for the further functionalization of the resulting 1,3-diketones. In addition, heterocyclic compounds, such as thiophenes and pyridines, were equally adaptable to the applied reaction conditions and formed the carbonylated a-arylation products 16 and 17 in good yields.…”

Recyclable Polymer-Supported Terpyridine–Palladium Complex for the Tandem Aminocarbonylation of Aryl Iodides to Primary Amides in Water Using NaN3 as Ammonia Equivalent

“…Water was deionized with a Millipore Milli-Q Gradient A10 system (Millipore, Bedford, MA, USA). NMR spectra were recorded on a Bruker AVANCE spectrometer (400 MHz for 1 H and 100 MHz for 13 C, Bruker, Karsruhe, Germany); 1 H and 13 C spectra were recorded in dimethyl sulfoxide-d 6 (DMSO-d 6 ) at 25 • C. Chemical shifts of 13 C are given relative to CDCl 3 and DMSO-d 6 as internal standards (δ 39.7 ppm). Mass spectra were measured on a JEOL JMS-T100GCv MS detector (GC-MS, JEOL, Tokyo, Japan) and a JEOL JMS-T100LP MS detector (LC-MS, JEOL); the base peak is denoted as "bp."…”

“…With regard to the Heck carbonylation reaction, aminocarbonylation reactions have also been developed as an alternative to the preparation of secondary or tertiary amides, as described in [11]. In 2010, Beller and co-workers developed the palladium-catalyzed synthesis of primary amides using carbon monoxide and ammonia [12,13]. This reaction used gaseous ammonia and Pd(OAc) 2 /dppf or Pd(OAc) 2 /nBuP(1-Adamantyl) 2 as the catalytic system.…”

CHAPTER 5. Ancillary Ligand Design in the Development of Palladium Catalysts for Challenging Selective Monoarylation Reactions

“…Although formally beyond the scope of this review, it is worthy of mention that carbonylative variants of such ammonia monoarylation reactions have also emerged that offer a novel entry point to the construction of primary aromatic amides from (hetero)aryl halides, carbon monoxide and ammonia. [48][49][50][51] The identification of useful catalysts for ammonia monoarylation laid the groundwork for the development of previously unknown BHA reactions involving the selective monoarylation of hydrazine with (hetero)aryl (pseudo)halides.…”