Special Issue "Transition-Metal Catalysts for C–H Bond Functionalization of Heteroarenes"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: 15 August 2020.

Special Issue Editor

Dr. Corinne Fruit
Website
Guest Editor
Normandie Univ, UNIROUEN, INSA Rouen, CNRS,COBRA UMR 6014, Rouen, France
Interests: heteroarenes; organometallic chemistry; C–H activation; catalysis; kinases inhibitors; Alzheimer’s disease; antitumoral activities

Special Issue Information

Dear Colleagues,

C–C and C–X bond formation from direct C–H activation is now recognized as a powerful and straightforward strategy for the synthesis of complex molecules, and especially for late-stage functionalization. Many of these reactions allow a streamlined route to new functionalized heterocycle compounds. This Special Issue focuses on the site-selective C–H functionalization of heteroarenes for the formation of new bonds such as carbon–carbon and carbon–heteroatom (nitrogen, oxygen, sulfur, boron, fluorine, etc.). The late-stage functionalization applied to the synthesis of arrays of potential bioactive compounds is of great interest, as well as the synthesis of new organic materials. Communications, articles, and reviews dedicated to recent advances in this area are welcome. In addition, the enhancement of the reactions based on advances in technologies such as microwave and flow systems will be included.

Dr. Corinne Fruit
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Metal catalysis
  • C–H activation
  • C–C bond formation
  • C–X bond formation
  • Heteroaromatic
  • Site-selectivity
  • Late-stage functionalization
  • Microwave irradiation
  • Environmental catalysis
  • Organic material

Published Papers (3 papers)

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Research

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Open AccessArticle
Radical C–H 18F-Difluoromethylation of Heteroarenes with [18F]Difluoromethyl Heteroaryl-Sulfones by Visible Light Photoredox Catalysis
Catalysts 2020, 10(3), 275; https://doi.org/10.3390/catal10030275 - 01 Mar 2020
Abstract
The 18F-labeling of CF2H groups has been recently studied in radiopharmaceutical chemistry owing to the favorable nuclear and physical characteristics of the radioisotope 18F for positron emission tomography (PET). Following up on the reported efficiency of the [18 [...] Read more.
The 18F-labeling of CF2H groups has been recently studied in radiopharmaceutical chemistry owing to the favorable nuclear and physical characteristics of the radioisotope 18F for positron emission tomography (PET). Following up on the reported efficiency of the [18F]difluoromethyl benzothiazolyl-sulfone ([18F]1) as a 18F-difluoromethylating reagent, we investigated the influence of structurally-related [18F]difluoromethyl heteroaryl-sulfones in the reactivity toward the photoredox C–H 18F-difluoromethylation of heteroarenes under continuous-flow conditions. In the present work, six new [18F]difluoromethyl heteroaryl-sulfones [18F]5a[18F]5f were prepared and, based on the overall radiochemical yields (RCYs), three of these reagents ([18F]5a, [18F]5c, and [18F]5f) were selected for the fully automated radiosynthesis on a FASTlabTM synthesizer (GE Healthcare) at high level of starting radioactivity. Subsequently, their efficiency as 18F-difluoromethylating reagents was evaluated using the antiherpetic drug acyclovir as a model substrate. Our results showed that the introduction of molecular modifications in the structure of [18F]1 influenced the amount of fac-IrIII(ppy)3 and the residence time needed to ensure a complete C–H 18F-difluoromethylation process. The photocatalytic C–H 18F-difluoromethylation reaction with the reagents [18F]5a, [18F]5c, and [18F]5f was extended to other heteroarenes. Radical-trapping experiments demonstrated the likely involvement of radical species in the C–H 18F-difluoromethylation process. Full article
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Review

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Open AccessFeature PaperReview
Pd-Catalyzed Intermolecular Dehydrogenative Heck Reactions of Five-Membered Heteroarenes
Catalysts 2020, 10(5), 571; https://doi.org/10.3390/catal10050571 - 19 May 2020
Abstract
The Pd-mediated cross-coupling of (hetero)arenes with alkenes may be an effective method for the formation of a C–C bond from two C–H bonds. Discovered by Fujiwara and co-workers in 1967, this reaction led to a number of reports that we firstly highlighted in [...] Read more.
The Pd-mediated cross-coupling of (hetero)arenes with alkenes may be an effective method for the formation of a C–C bond from two C–H bonds. Discovered by Fujiwara and co-workers in 1967, this reaction led to a number of reports that we firstly highlighted in 2011 (review with references till June 2010) and for which, we retained the name “dehydrogenative Heck reaction”. The topic, especially the reactions of five-membered heteroarenes, has been the subject of intensive research over the last ten years. The present review is limited to these dehydrogenative Heck reactions published since 2010, underlining the progress of the procedures. Full article
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Open AccessFeature PaperReview
Diaryliodoniums Salts as Coupling Partners for Transition-Metal Catalyzed C- and N-Arylation of Heteroarenes
Catalysts 2020, 10(5), 483; https://doi.org/10.3390/catal10050483 - 28 Apr 2020
Abstract
Owing to the pioneering works performed on the metal-catalyzed sp2 C–H arylation of indole and pyrrole by Sanford and Gaunt, N– and C-arylation involving diaryliodonium salts offers an attractive complementary strategy for the late-stage diversification of heteroarenes. The main feature of [...] Read more.
Owing to the pioneering works performed on the metal-catalyzed sp2 C–H arylation of indole and pyrrole by Sanford and Gaunt, N– and C-arylation involving diaryliodonium salts offers an attractive complementary strategy for the late-stage diversification of heteroarenes. The main feature of this expanding methodology is the selective incorporation of structural diversity into complex molecules which usually have several C–H bonds and/or N–H bonds with high tolerance to functional groups and under mild conditions. This review summarizes the main recent achievements reported in transition-metal-catalyzed N– and/or C–H arylation of heteroarenes using acyclic diaryliodonium salts as coupling partners. Full article
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Pd-catalyzed intermolecular dehydrogenative Heck reactions of five membered heteroarenes
Authors: Jacques Muzart
Affiliation: CNRS - Université de Reims Champagne-Ardenne, Institut de Chimie Moléculaire de Reims, UFR des Sciences Exactes et Naturelles, 51687 Reims Cedex 2, France
Abstract: The Pd-mediated cross coupling of (hetero)arenes with alkenes may be an effective method for the formation of a C-C bond from two C-H. Discovered by Fujiwara and co-workers in 1967, this reaction has led to number of reports that we firstly highlighted in 2011 (review with references till June 2010) and for which, we retained the name “dehydrogenative Heck reaction”. The topic, especially the reactions of five membered heteroarenes, has been the subject of intensive research over the last ten years. The present review is limited to these dehydrogenative Heck reactions published since 2010, underlining the progress of the procedures.

Title: The effect of ligand in palladium catalyzed formation of 2-(hetero)arylaminooxazoles and 4-(hetero)arylaminothiazoles: a theoretical research
Authors: Bo-Long Liu, Gao-Li Zhao, Bin-Bin Xie, Cheng-Xing Cui
Affiliation: Zhejiang Normal University, Henan Institute of Science and Technology
Abstract: The Palladium-catalyzed C-N bond formation is of great importance in the synthesis of nitrogen-containing molecules. The BrettPhos ligand is an effective supporting for the selective mono-arylation of primary amines as catalyzed by palladium, which includes C- and O- bound forms. However, the C-bound complex is more competent for reductive elimination than the O-bound one. Recently, an array of ligands that could decrease the percentage of the O-bound isomer (Angew. Chem. Int. Ed. 2017, 56, 10569 –10572 ) were developed. This ligand was experimentally observed to be effective for the cross-coupling of oxazolamine with an array of aryl chlorides and bromides. Herein, we provide a systematic investigation about the mechanisms of this catalyzed reaction. Two possible reaction pathways were proposed and calculated with the newly developed functional, MN15L, which is proved to be very reliable for the investigation of systems containing transition metals. The calculated results were analyzed and prepared from different perspectives. We think this contribution could provide some newly points of view for the development of novel Pd-ligand for the C-H bond functionalization of heteroarenes.

Title: Syntheses of 3,3-disubstituted Dihydrobenzofurans, Indolines, Indolinones and Isochromanes by Palladium-Catalyzed Tandem Reaction using Pd(PPh3)2Cl2/(±)-BINAP as a Catalytic System
Authors: Guizhou Yue, *a‡ Zhengjie Dou,a‡ Gang Ding,b Yao Wu,a Huabao Chen,b Zhongqiong Yin,c Xu Song,c ChangLiang He,c Xianxiang Wang,a Xiaoxia Liangc and Cuifen Lu*d
Affiliation: a.College of Science, Sichuan Agricultural University, Ya’an, Sichuan, 625014, China. E-mail: [email protected] b.College of Agricultural Sciences, Sichuan Agricultural University, Chengdu, Sichuan, 611130, China. c.College of Veterinary Medicine, Sichuan Agricultural University, Chengdu, Sichuan, 611130, China. d.Hubei Collaborative Innovation Center for Advanced Organochemical Materials & Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Hubei University, Wuhan 430062, China. E-mail: [email protected]
Abstract: A general procedure for the tandem arylation reaction of arylbromide with heteroaryl compounds was developed by using Pd(PPh3)2Cl2/(±)-BINAP as catalytic system. Both sulphur- and oxygen-containing heterocycles were also employed as an efficient reagent for arylation, which gave moderate to excellent yields with moderate to good regioselectivties. Different from the previous study, this type of tandem reaction was expanded to synthesize isochromanes. The synthesized new compounds were well characterized through different spectroscopic techniques, such as 1H and 13C NMR, and mass spectral analysis.

Title: Diaryliodoniums Salts as Coupling Partners for Transition-Metal Catalyzed C- and N-Arylation of Heteroarenes
Authors: Alexandra Pacheco-Benichou, Thierry Besson and Corinne Fruit
Affiliation: Normandie Univ, UNIROUEN, INSA Rouen, CNRS, COBRA UMR 6014, F-76000 Rouen, France
Abstract: Owing to the pioneering works performed on the metal-catalyzed sp2 C-H arylation of indole and pyrrole by Sanford and Gaunt, N- and C-arylation involving diaryliodonium salts offers an attractive complementary strategy for the late-stage diversification of heteroarenes. The main feature of this expanding methodology is the incorporation of structural diversity into complex molecules having usually several C-H bonds and/or N-H bonds with high tolerance to functional groups. This review summarizes the main recent achievements reported in transition-metal-catalyzed N- and/or C-H arylation of heteroarenes using acyclic diaryliodoniums as coupling partners.

Title: Copper-Catalyzed C-H Arylation of Heteroarenes using Diaryliodoniums Salts
Authors: Corinne Fruit
Affiliation: Normandie Univ, UNIROUEN, INSA Rouen, CNRS,COBRA UMR 6014, Rouen, France

Title: Recent Advances in C–S bond formation of Indoles
Authors: Liang-Hua Zou*
Affiliation: The Key Laboratory of Carbohydrate Chemistry and Biotechnology, Ministry of Education, School of Pharmaceutical Sciences, Jiangnan University, Lihu Avenue 1800, Wuxi 214122, China
Abstract: The research on the synthesis of indoles has been extensively investigated during the past years due to their significant properties and application. The functionalization of indole includes various bond formations, such as C–C bond, C–N bond, C–O bond, C–S bond, and so on. During the past few decades, C–H activation has attracted significant attention because of several appealing features, such as atom economy, high step economy and synthetic practicality. As regarding to C-H activation of indoles, there are six C–H bonds in indole core including C2 to C3 (pyrrole core) and C4-C7 (benzene core) positions that can be functionalized. Recently, our group has developed several protocols for the C–S bond formation of indoles. Therefore, this mini-review will focus on the advances in C–S bond formation of indoles in the past 10 years.

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