79606-45-4Relevant academic research and scientific papers
Cu-catalyzed arylation of bromo-difluoro-acetamides by aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts: New entries to aromatic amides
Iaroshenko, Viktor O.,Jakubczyk, Micha?,Lanka, Suneel,Mkrtchyan, Satenik,Pittelkow, Michael
, (2021/06/12)
We describe a mechanism-guided discovery of a synthetic methodology that enables the preparation of aromatic amides from 2-bromo-2, 2-difluoroacetamides utilizing a copper-catalyzed direct arylation. Readily available and structurally simple aryl precursors such as aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts were used as the source for the aryl substituents. The scope of the reactions was tested, and the reactions were insensitive to the electronic nature of the aryl groups, as both electron-rich and electron-deficient aryls were successfully introduced. A wide range of 2-bromo-2, 2-difluoroacetamides as either aliphatic or aromatic secondary or tertiary amides were also reactive under the developed conditions. The described synthetic protocols displayed excellent efficiency and were successfully utilized for the expeditious preparation of diverse aromatic amides in good-to-excellent yields. The reactions were scaled up to gram quantities.
Remarkably Efficient Iridium Catalysts for Directed C(sp2)-H and C(sp3)-H Borylation of Diverse Classes of Substrates
Chattopadhyay, Buddhadeb,Hassan, Mirja Md Mahamudul,Hoque, Md Emdadul
, p. 5022 - 5037 (2021/05/04)
Here we describe the discovery of a new class of C-H borylation catalysts and their use for regioselective C-H borylation of aromatic, heteroaromatic, and aliphatic systems. The new catalysts have Ir-C(thienyl) or Ir-C(furyl) anionic ligands instead of the diamine-type neutral chelating ligands used in the standard C-H borylation conditions. It is reported that the employment of these newly discovered catalysts show excellent reactivity and ortho-selectivity for diverse classes of aromatic substrates with high isolated yields. Moreover, the catalysts proved to be efficient for a wide number of aliphatic substrates for selective C(sp3)-H bond borylations. Heterocyclic molecules are selectively borylated using the inherently elevated reactivity of the C-H bonds. A number of late-stage C-H functionalization have been described using the same catalysts. Furthermore, we show that one of the catalysts could be used even in open air for the C(sp2)-H and C(sp3)-H borylations enabling the method more general. Preliminary mechanistic studies suggest that the active catalytic intermediate is the Ir(bis)boryl complex, and the attached ligand acts as bidentate ligand. Collectively, this study underlines the discovery of new class of C-H borylation catalysts that should find wide application in the context of C-H functionalization chemistry.
Visible-Light-Induced, Base-Promoted Transition-Metal-Free Dehalogenation of Aryl Fluorides, Chlorides, Bromides, and Iodides
Ding, Ting-Hui,Qu, Jian-Ping,Kang, Yan-Biao
supporting information, p. 3084 - 3088 (2020/04/10)
We report a simple and efficient visible-light-induced transition-metal-free hydrogenation of aryl halides. The combined visible light and base system is used to initiate the desired radical-mediated hydrogenation. A variety of aryl fluorides, chlorides, bromides, and iodides could be reduced to the corresponding (hetero)arenes with excellent yields under mild conditions. Various functional groups and other heterocyclic compounds are tolerated.
Identification of key functionalization species in the Cp?Ir(iii)-catalyzed-: ortho halogenation of benzamides
Brown, Caleb A.,Guzmán Santiago, Alexis J.,Ison, Elon A.,Sommer, Roger D.
supporting information, p. 16166 - 16174 (2020/12/03)
Cp?Ir(iii) complexes have been shown to be effective for the halogenation of N,N-diisopropylbenzamides with N-halosuccinimide as a suitable halogen source. The optimized conditions for the iodination reaction consist of 0.5 mol% [Cp?IrCl2]2 in 1,2-dichlor
Amide Effects in C?H Activation: Noncovalent Interactions with L-Shaped Ligand for meta Borylation of Aromatic Amides
Bisht, Ranjana,Hoque, Md Emdadul,Chattopadhyay, Buddhadeb
, p. 15762 - 15766 (2018/11/10)
A new concept for the meta-selective borylation of aromatic amides is described. It has been demonstrated that while esters gave para borylations, amides lead to meta borylations. For achieving high meta selectivity, an L-shaped bifunctional ligand has been employed and engages in an O???K noncovalent interaction with the oxygen atom of the moderately distorted amide carbonyl group. This interaction provides exceptional control for meta C?H activation/borylation.
Alternative formation of amides and β-enaminones from aroyl chlorides using the TiCl4-trialkylamine reagent system
Leggio, Antonella,Comandè, Alessandra,Belsito, Emilia Lucia,Greco, Marianna,Lo Feudo, Lucia,Liguori, Angelo
, p. 5677 - 5683 (2018/08/17)
The TiCl4/NR3 reagent system has been successfully employed for the synthesis of amides and β-enaminones. The reaction of variously substituted benzoyl chlorides with the TiCl4/NR3 reagent system, by using two different experimental procedures (Method A and Method B), afforded alternatively the corresponding amides and β-enaminones as unique or major products. The two developed protocols were investigated with a series of tertiary amines. The reactions, modulated by the presence of TiCl4, provided the corresponding amides or β-enaminones with satisfactory yields. This paper reports a new method for carbon-carbon bond formation via the reaction of aroyl chlorides with the TiCl4/NR3 reagent system.
Direct Hydroxylation and Amination of Arenes via Deprotonative Cupration
Tezuka, Noriyuki,Shimojo, Kohei,Hirano, Keiichi,Komagawa, Shinsuke,Yoshida, Kengo,Wang, Chao,Miyamoto, Kazunori,Saito, Tatsuo,Takita, Ryo,Uchiyama, Masanobu
supporting information, p. 9166 - 9171 (2016/08/05)
Deprotonative directed ortho cupration of aromatic/heteroaromatic C-H bond and subsequent oxidation with t-BuOOH furnished functionalized phenols in high yields with high regio- and chemoselectivity. DFT calculations revealed that this hydroxylation reaction proceeds via a copper (I → III → I) redox mechanism. Application of this reaction to aromatic C-H amination using BnONH2 efficiently afforded the corresponding primary anilines. These reactions show broad scope and good functional group compatibility. Catalytic versions of these transformations are also demonstrated.
Rhodium-catalyzed direct coupling of benzothioamides with alkenes and alkynes through directed C-H bond cleavage
Yokoyama, Yuki,Unoh, Yuto,Bohmann, Rebekka Anna,Satoh, Tetsuya,Hirano, Koji,Bolm, Carsten,Miura, Masahiro
supporting information, p. 1104 - 1106 (2015/09/02)
Rhodium-catalyzed direct coupling of benzothioamides with alkenes proceeds smoothly involving ortho-CH bond cleavage. The thioamides also couple with alkynes under similar conditions accompanied by desulfurization and CN bond cleavage to produce indenone derivatives.
High-yielding, versatile, and practical [Rh(III)Cp*]-catalyzed ortho bromination and iodination of arenes
Schroeder, Nils,Wencel-Delord, Joanna,Glorius, Frank
supporting information; experimental part, p. 8298 - 8301 (2012/06/29)
We report a uniquely high-yielding, general, and practical ortho bromination and iodination reaction of different classes of aromatic compounds. This reaction occurs by Rh(III)-catalyzed C-H bond activation methodology and is therefore the first example of the application of this cationic catalyst for C-Br and C-I bond formation.
Manufacturing synthesis of 5-substituted phthalides
Faigl, Ferenc,Thurner, Angelika,Molnar, Balazs,Simig, Gyula,Volk, Balazs
experimental part, p. 617 - 622 (2011/07/09)
A manufacturing synthesis of 5-chlorophthalide has been elaborated. The key step of the procedure is ortho-lithiation of 4-chloro-N,N-diisopropylbenzamide, followed by formylation with dimethyl formamide. Reduction of the formyl moiety and subsequent ring
