Journal ArticleDOI
Site-selective and versatile aromatic C−H functionalization by thianthrenation
Florian Berger,Matthew B. Plutschack,Julian Riegger,Wanwan Yu,Samira Speicher,Matthew Ho,Nils Frank,Tobias Ritter +7 more
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TLDR
This transformation differs fundamentally from all previous aromatic C–H functionalization reactions in that it provides direct access to a large number of derivatives of complex small molecules, quickly generating functional diversity with selectivity that is not achievable by other methods.Abstract:
Direct C-H functionalization can quickly increase useful structural and functional molecular complexity1-3. Site selectivity can sometimes be achieved through appropriate directing groups or substitution patterns1-4-in the absence of such functionality, most aromatic C-H functionalization reactions provide more than one product isomer for most substrates1,4,5. Development of a C-H functionalization reaction that proceeds with high positional selectivity and installs a functional group that can serve as a synthetic linchpin for further functionalization would provide access to a large variety of well-defined arene derivatives. Here we report a highly selective aromatic C-H functionalization reaction that does not require a particular directing group or substitution pattern to achieve selectivity, and provides functionalized arenes that can participate in various transformations. We introduce a persistent sulfur-based radical to functionalize complex arenes with high selectivity and obtain thianthrenium salts that are ready to engage in different transformations, via both transition-metal and photoredox catalysis. This transformation differs fundamentally from all previous aromatic C-H functionalization reactions in that it provides direct access to a large number of derivatives of complex small molecules, quickly generating functional diversity with selectivity that is not achievable by other methods.read more
Citations
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Late-stage C-H functionalization offers new opportunities in drug discovery
TL;DR: In this paper, the authors provide a toolbox for chemists in academia as well as industrial practitioners, and introduce guiding principles for the application of late-stage functionalization strategies to access new molecules of interest.
Journal ArticleDOI
Arene diversification through distal C(sp2)-H functionalization.
TL;DR: In this article, the authors summarize the recent elegant discoveries exploiting directing group assistance, transient mediators or traceless directors, noncovalent interactions, and catalyst and/or ligand selection to control distal C-H activation.
Journal ArticleDOI
Methodologies and Strategies for Selective Borylation of C–Het and C–C Bonds
Minyan Wang,Zhuangzhi Shi +1 more
TL;DR: A comprehensive overview of the direct borylation of less reactive C-Het and C-C bonds has become highly important to get efficiency and functional-group compatibility in organoborons.
Journal ArticleDOI
Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds.
Rolando Cannalire,Sveva Pelliccia,Luca Sancineto,Ettore Novellino,Gian Cesare Tron,Mariateresa Giustiniano +5 more
TL;DR: In this paper, the authors present a review of the recent developments in the field of late stage functionalization of complex biorelevant compounds and highlight the expected future progress and potential applications.
Journal ArticleDOI
Photoredox catalysis with aryl sulfonium salts enables site-selective late-stage fluorination
Jiakun Li,Junting Chen,Ruocheng Sang,Won-Seok Ham,Matthew B. Plutschack,Florian Berger,Sonia Chabbra,Alexander Schnegg,Christophe Genicot,Tobias Ritter +9 more
TL;DR: It has now been shown that aryl sulfonium salts, which can be made by site-selective C–H functionalization, have advantageous photoredox reactivity compared to conventional (pseudo)halides and can be used for late-stage C-H fluorination.
References
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Ion radicals. XXIX. Reaction of thianthrene cation radical perchlorate with some benzene derivatives
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Zwitterionic-Salt-Catalyzed Site-Selective Monobromination of Arenes.
TL;DR: A zwitterionic-salt-catalyzed electrophilic monobromination of arenes with high regioselectivity has been developed and under mild reaction conditions, a wide range ofmonobrominated aromatic compounds can be obtained in excellent yields.
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Ion radicals. XXV. Reactions of thianthrene and phenothiazine perchlorates with nitrite ion, pyridine, and other nucleophiles
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A Convenient Route to Diverse Heterocycles through an Addition of β-Amino Carbonyl Compounds to 3-Halogeno-4-methoxybenzynes
TL;DR: 3-Halogeno-4-methoxybenzynes 5 generated from 5-(3-halogeno,4,methoxyphenyl)thianthrenium perchlorates 1 and LDA in THF at reflux reacted with various beta-amino carbonyl compounds and 2-aminophenyl benzenesulfonate etc. to give diverse heterocyclic compounds.
Journal ArticleDOI
Substituted Dipyridylethenes and -ethynes and Key Pyridine Building Blocks
TL;DR: In this paper, various 2,5-disubstituted pyridines were obtained by reduction of the nicotinic acid 3, hydrolysis of the bis(morpholino)methylpyridine 6 or the reaction of 5-bromopyridine 12 and 14 with lithium butoxide in DMF.