Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

• Kirk W. Shimkin and
• Donald A. Watson

Beilstein J. Org. Chem. 2015, 11, 2278–2288, doi:10.3762/bjoc.11.248

• catalyzed C–H amination reactions, as reported by Warren and co-workers [27][28]. Using this mild copper-catalyzed system, β-arylnitroalkanes were produced in excellent yields (Scheme 3) [16]. The scope of this transformation is remarkably broad with respect to both coupling partners. Electron-rich

Recent advances in copper-catalyzed C–H bond amidation

• Jie-Ping Wan and
• Yanfeng Jing

Beilstein J. Org. Chem. 2015, 11, 2209–2222, doi:10.3762/bjoc.11.240

• sulfonamidation of 2-arylpyridines via C–H activation. Besides the peroxide-free advantage, the C–H amination using aniline was found applicable to allow the synthesis of biarylamine. More recently, based on the DG strategy, the Yu group [59] designed the o-amidation of arylamides with copper catalysis under

• and benzene C–H bonds. Copper-catalyzed C–H amination/amidation of quinoline N-oxides. Copper-catalyzed aldehyde formyl C–H amidation. Copper-catalyzed formamide C–H amidation. Copper-catalyzed sulfonamidation of vinyl C–H bonds. CuCl2-catalyzed amidation/sulfonamidation of alkynyl C–H bonds. Cu(OH)2

C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• alkenes via C–H cleavage is much less known in literature. In 2014, Yu and co-workers [66] reported the cascade synthesis of functionalized pyrrolones 66 via the dual C–H functionalization of α-alkenoylketene N,S-acetals 65. The construction of the products involved the oxidative alkene C–H amination and

Copper-catalyzed aerobic radical C–C bond cleavage of N–H ketimines

• Ya Lin Tnay,
• Gim Yean Ang and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2015, 11, 1933–1943, doi:10.3762/bjoc.11.209

• found to undergo copper-catalyzed aerobic aromatic C–H amination (Scheme 3a) [52] or 1,4-aminooxygenation (spirocyclization) (Scheme 3b) [51], affording phenanthridine derivatives and azaspirocyclohexadienones, respectively, depending on the helical sense of the biaryl axis. Herein we report

Come-back of phenanthridine and phenanthridinium derivatives in the 21st century

• Lidija-Marija Tumir,
• Marijana Radić Stojković and
• Ivo Piantanida

Beilstein J. Org. Chem. 2014, 10, 2930–2954, doi:10.3762/bjoc.10.312

• second step under the catalysis of Pd(OAc)2 comprised both cyclisation and oxidation in a single step: a dehydrogenative C–H amination with PhI(OAc)2 as oxidant and removal of the picolinamide group followed by oxidation with Cu(OAc)2. This strategy afforded phenanthridines in moderate to good yields (up

Silver and gold-catalyzed multicomponent reactions

• Giorgio Abbiati and
• Elisabetta Rossi

Beilstein J. Org. Chem. 2014, 10, 481–513, doi:10.3762/bjoc.10.46

• R4 was an o-azidobenzene group by a RuCl3 catalyzed C–H amination (Scheme 12, path B). As explained above, A3-MCR is a reaction in which the formation of a metal acetylide and its reaction with an in situ formed iminium cation are the key steps of the process. In the recent literature, there are

Synthesis of phenanthridines via palladium-catalyzed picolinamide-directed sequential C–H functionalization

• Ryan Pearson,
• Shuyu Zhang,
• Gang He,
• Nicola Edwards and
• Gong Chen

Beilstein J. Org. Chem. 2013, 9, 891–899, doi:10.3762/bjoc.9.102

• bond of benzylpicolinamides is first arylated with an aryl iodide. The resulting biaryl compound is then subjected to palladium-catalyzed picolinamide-directed intramolecular dehydrogenative C–H amination with PhI(OAc)2 oxidant to form the corresponding cyclized dihydrophenanthridines. The benzylic

• [26]. In 2012, our laboratory [28] as well as that of Daugulis [27] independently reported that picolinamide substrates can undergo intramolecular dehydrogenative C–H amination reactions to afford medium-sized N-heterocycles under the catalysis of Pd(OAc)2 with PhI(OAc)2 oxidant. These discoveries led

• dihydrophenanthridines, which could be further converted to phenanthridine products under oxidative conditions. Ideally, we hoped to perform both the intramolecular C–H amination and subsequent oxidation in a single step [36]. Arylation of 2-methoxybenzyl picolinamide 1 with 4-iodoanisole (2) under various conditions