2413-02-7Relevant articles and documents
Site-Selective Arylation of Naphthalenes: a Key Entry towards Extended Fluorenones and Phenanthridinones
Large, Benjamin,Gigant, Nicolas,Joseph, Delphine,Clavier, Gilles,Prim, Damien
, p. 1835 - 1841 (2019)
The development of an oriented arylation process dedicated to the naphthalene core is presented. Our approach is based on dual role of N-tosyl carboxamides acting jointly as a directing group in a first C–H arylation step and as a “CO” or “CO–NH” fragment
Organocatalyst in Direct C(sp2)-H Arylation of Unactivated Arenes: [1-(2-Hydroxyethyl)-piperazine]-Catalyzed Inter-/Intra-molecular C-H Bond Activation
Yadav, Lalit,Tiwari, Mohit K.,Shyamlal, Bharti Rajesh Kumar,Chaudhary, Sandeep
, p. 8121 - 8141 (2020/07/16)
This article describes the identification of 1-(2-hydroxyethyl)-piperazine as a new, cost-effective, highly efficient organocatalyst, which promotes both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in the presence of potassium tert-butoxide. While the inter-molecular C-H arylation of unactivated benzenes with aryl halides (Ar-X; X = I, Br, Cl) toward biaryl syntheses underwent smoothly in the presence of only 10 mol percent organocatalyst, the intra-molecular C-H arylation catalytic system composed of 40 mol percent each of the catalyst and the additive (4-dimethylaminopyridine (DMAP)). The novel catalyst was also able to perform both inter- A nd intra-molecular direct arylations simultaneously in a single pot. The mechanistic studies confirmed the involvement of aryl radical anions and proceeded via a single-electron-transfer (SET) mechanism. The large substrate scope, high functional group tolerance, competition experiments, gram-scale synthesis, and kinetic studies further highlight the importance and versatile nature of the methodology as well as the compatibility of the new catalyst. To the best of our knowledge, this is the first report on any organocatalyst that reported detailed investigations of both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in a single representation.
Rhodium(I)-Catalyzed Aryl C-H Carboxylation of 2-Arylanilines with CO2
Gao, Yuzhen,Cai, Zhihua,Li, Shangda,Li, Gang
supporting information, p. 3663 - 3669 (2019/05/17)
An unprecedented Rh(I)-catalyzed, amino-group-assisted C-H carboxylation of 2-arylanilines with CO2 under redox-neutral conditions has been developed. This reaction was promoted by a phosphine ligand with t-BuOK as the base and did not require the use of additional strong organometallic reagent. It enabled an efficient direct conversion of a broad range of 2-(hetero)arylanilines including electron-deficient heteroarenes to various phenanthridinones. Possible intermediates of the reaction were also evaluated in the preliminary mechanistic studies.
Pd(II)-catalyzed C(sp2)-H carbonylation of biaryl-2-amine: Synthesis of phenanthridinones
Liang, Zunjun,Zhang, Jitan,Liu, Zhanxiang,Wang, Kai,Zhang, Yuhong
, p. 6519 - 6526 (2013/07/26)
A Pd(OAc)2-catalyzed C(sp2)-H carbonylation protocol of arenes under carbon monoxide atmosphere has been developed. The scope of the carbonylation reaction is broad and tolerates a variety of useful functional groups. This reaction provides a novel and efficient method for the synthesis of biologically and pharmaceutically significant phenanthridinones.
KOtBu mediated synthesis of phenanthridinones and dibenzoazepinones
Bhakuni, Bhagat Singh,Kumar, Amit,Balkrishna, Shah Jaimin,Sheikh, Javeed Ahmed,Konar, Sanjit,Kumar, Sangit
supporting information; experimental part, p. 2838 - 2841 (2012/07/28)
Synthesis of substituted phenanthridinones and dibenzoazepinones has been realized from 2-halo-benzamides in the presence of potassium tert-butoxide and a catalytic amount of 1,10-phenanthroline or AIBN. This new carbon-carbon bond forming reaction gives direct access to various biaryl lactams containing six- and seven-membered rings chemoselectively. Carbon-carbon coupling seems to proceed by the generation of a radical in the amide ring which leads to C-H arylation of aniline.
