Recent Achievements in the Copper-Catalyzed Arylation of Adamantane-Containing Amines, Di- and Polyamines

Abstract

Rapid development of the copper-catalyzed amination of aryl halides in the beginning of the 21st century, known as the Renaissance of the Ullmann chemistry, laid foundations for the use of this method as a powerful tool for the construction of the C(sp2)-N bond and became a rival of the Buchwald–Hartwig amination reaction. Various applications of this approach are well-documented in a number of comprehensive and more specialized reviews, and this overview in the form of a personal account of the Cu-catalyzed arylation and heteroarylation of the adamantane-containing amines, and di- and polyamines, covers a more specific area, showing the possibilities of the method and outlining general regularities, considering reagents structure, copper source and ligands, scope, and limitations. The material of the last decade is mainly considered, and recent data on the application of the unsupported copper nanoparticles and possibilities of the Chan-Lam reaction as an alternative to the use of aryl halides are also discussed.

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…C6F5SnCl3, (SiMe3)2S / C6H6, 10 °C, 15 min D [319] [{(Me3Si)3CSn}4S6] (597) [(Me3Si)3CSnBr3], Na2S / NH3, 24 h D [317] [(StySn)4S6] (598)…”

“…[594] Functional group transformations involve converting one functional group into another while preserving the overall molecular structure, such as the adamantane core. [565,569,569,[595][596][597] Developing efficient and selective methods for functional group transformations encompasses a wide array of chemical reactions. These reactions can include substitution, [598][599][600][601] addition, [602] and elimination reactions, [603][604][605] among others.…”

NQNHC Ligand-Enabled Cu(I)-Catalyzed Double Hydroamination: A Regio- and Chemoselective Bicyclization of o-Amino 1,6-Diyne

“…7,9 Therefore, to overcome these challenges, we envisioned that a copper(I) catalyst could drive this transformation due to its mild electrophilicity and affinity for amine functional groups. 10 With this objective, we have employed a substrate that could undergo copper-catalyzed double hydroamination, which afforded a bioactive oxazino [4,3-a]indole skeleton via bicyclization (Figure 2c). The major challenges with the employed substrate are in the second cyclization step viz C−C versus C−N bond formation; previously, Fujii and Ohno realized carbocyclization over the second hydroamination utilizing a Au(I) catalyst.…”

“…However, copper-catalyzed hydroamination could be a promising approach, as it has been documented in the literature by Buchwald et al (Figure a) . The copper catalyst has been found to be effective for single-hydroamination reactions, but the double hydroamination of the alkyne is still challenging and underdeveloped, as it is not been explored either intermolecularly or intramolecularly (Figure b). , Therefore, to overcome these challenges, we envisioned that a copper­(I) catalyst could drive this transformation due to its mild electrophilicity and affinity for amine functional groups . With this objective, we have employed a substrate that could undergo copper-catalyzed double hydroamination, which afforded a bioactive oxazino­[4,3- a ]­indole skeleton via bicyclization (Figure c).…”

Synthesis and Applications of Copper-Based Catalysts

“…At the beginning of the 21st century, the fast development of the copper-catalyzed amination of aryl halides provided an efficient approach to constructing the C(sp 2 )-N bond, which competed against the classic Buchwald-Hartwig amination reaction. Averin et al [8] reviewed recent progress in the copper-catalyzed arylation and heteroarylation of adamantanecontaining amines, diamines, and polyamines. With the primary purpose of classifying the dimension and limitation of the copper catalysis involved in the arylation and heteroarylation of the as-mentioned amines, this review addressed the following issues: the dependence of the most suitable catalytic systems on the property of reagents, the chance of N,N -di(hetero) arylation of the diamines, oxadiamines, and polyamines, the utilization of unsupported copper nanoparticles, and the feather of the Chan-Lam amination using adamantane-containing amines, diamines, and oxadiamines.…”