The Directed Ortho Metalation−Ullmann Connection. A New Cu(I)-Catalyzed Variant for the Synthesis of Substituted Diaryl Ethers

Modern Synthetic Methods for Copper‐Mediated C(aryl)O, C(aryl)N, and C(aryl)S Bond Formation

“…(29)]. [82] The methodology employed the catalytic (5 mol %) use of [CuPF 6 (MeCN) 4 ] instead of the air-sensitive (CuOTf) 2 ·C 6 H 6 along with Cs 2 CO 3 in boiling toluene or xylenes. This protocol allowed the preparation of a range of products (Scheme 73) from aryl iodides, bromides, and even secondary chloro benzamides, which are reported to be poor substrates for the Ullmann condensation.…”

Application of n.c.a. 4‐[18F]fluorophenol in diaryl ether syntheses of 2‐(4‐[18F]fluorophenoxy)‐benzylamines

“…radiochemistry of this study. In contrast, the recently suggested catalyst tetrakis(acetonitrile)copper(I) hexafluorophosphate 31 8 with slight modifications. An overall radiochemical yield of 65 AE 3% could be achieved.…”

“…Scheme 2). However, an application of the water sensitive tetrakis(acetonitrile)copper(I) hexafluorophosphate catalyst 31 was successful, using toluene or xylene as solvent in a sealed vessel with a reaction temperature of 1108C. This allowed to decrease the reaction time to 25 min.…”

The Directed Ortho Metallation (DoM)–Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl–Aryl and Aryl–Heteroatom–Aryl Bonds

“…The picture here may be incomplete in view of the significant amount of this type of chemistry that is being pursued in the pharmaceutical industry. In the inverted HetArB(OH) 2 -ArLG series (entries 11,12), the work on indoles highlights the potential of the DoM-cross-coupling methodology in this underexplored area [28c]. Studies on the ArB(OH) 2 -6-ring HetArLG group (Table 14.6) [48][49][50][51][52][53][54][55] show the not-surprising dominance of pyridines (entries 1-8) some of which, bearing dihalogen substitution patterns, provide cross-coupling selectivity and hence interesting azabiaryls for further manipulation (entries 3, 7).…”