62926-84-5Relevant articles and documents
Photo-Ni-Dual-Catalytic C(sp2)-C(sp3) Cross-Coupling Reactions with Mesoporous Graphitic Carbon Nitride as a Heterogeneous Organic Semiconductor Photocatalyst
Antonietti, Markus,Ghosh, Indrajit,K?nig, Burkhard,Khamrai, Jagadish,Savateev, Aleksandr
, p. 3526 - 3532 (2020/04/09)
The synergistic combination of a heterogeneous organic semiconductor mesoporous graphitic carbon nitride (mpg-CN) and a homogeneous nickel catalyst with visible-light irradiation at room temperature affords the C(sp2)-C(sp3) cross-co
Aminoalkyl radicals as halogen-atom transfer agents for activation of alkyl and aryl halides
Constantin, Timothée,Juliá, Fabio,Leonori, Daniele,Regni, Alessio,Sheikh, Nadeem S.,Zanini, Margherita
, p. 1021 - 1026 (2020/03/10)
Organic halides are important building blocks in synthesis, but their use in (photo)redox chemistry is limited by their low reduction potentials. Halogen-atom transfer remains the most reliable approach to exploit these substrates in radical processes despite its requirement for hazardous reagents and initiators such as tributyltin hydride. In this study, we demonstrate that a-aminoalkyl radicals, easily accessible from simple amines, promote the homolytic activation of carbon-halogen bonds with a reactivity profile mirroring that of classical tin radicals. This strategy conveniently engages alkyl and aryl halides in a wide range of redox transformations to construct sp3-sp3, sp3-sp2, and sp2-sp2 carbon-carbon bonds under mild conditions with high chemoselectivity.
Thiyl radical promoted chemo- and regioselective oxidation of CC bonds using molecular oxygen: Via iron catalysis
Xiong, Baojian,Zeng, Xiaoqin,Geng, Shasha,Chen, Shuo,He, Yun,Feng, Zhang
supporting information, p. 4521 - 4527 (2018/10/17)
The first example of the thiyl radical promoted ligand-free iron-catalyzed oxidative cleavage of alkenes using molecular oxygen (1 atm) has been developed. The reaction proceeds under mild reaction conditions with high efficiency and high chemo- and regioselectivity. It features a broad substrate scope and excellent functional group compatibility, enabling facile access to valuable molecules for application in medicinal chemistry. Preliminary mechanistic studies reveal that a vital intermediate dioxetane might be involved in the reaction and a thiyl radical plays a synergistic role in facilitating the selective oxidation of the CC bond.
Catalytic Oxidative Trifluoromethoxylation of Allylic C?H Bonds Using a Palladium Catalyst
Qi, Xiaoxu,Chen, Pinhong,Liu, Guosheng
supporting information, p. 9517 - 9521 (2017/08/01)
A catalytic intermolecular allylic C?H trifluoromethoxylation reaction of alkenes has been developed based on the use of a palladium catalyst, CsOCF3 as the trifluoromethoxide source, and benzoquinone as the oxidant. This reaction provides an efficient route for directly accessing allylic trifluoromethoxy derivatives with excellent regioselectivities from terminal alkenes via an allylic C?H bond activation process.
Cross-Coupling Reactions of Aryldiazonium Salts with Allylsilanes under Merged Gold/Visible-Light Photoredox Catalysis
Akram, Manjur O.,Mali, Pramod S.,Patil, Nitin T.
supporting information, p. 3075 - 3078 (2017/06/23)
A method for the cross-coupling reactions of aryldiazonium salts with trialkylallylsilanes via merged gold/photoredox catalysis is described. The reaction is proposed to proceed through a photoredox-promoted generation of an electrophilic arylgold(III) intermediate that undergoes transmetalation with allyltrimethylsilane to form allylarenes.
Palladium-catalyzed regioselective azidation of allylic C-H bonds under atmospheric pressure of dioxygen
Chen, Huoji,Yang, Wanfei,Wu, Wanqing,Jiang, Huanfeng
supporting information, p. 3340 - 3343 (2014/05/20)
A palladium-catalyzed allylic azidation of alkenes with sodium azide under atmospheric pressure of dioxygen was developed. This methodology provides a new efficient and simple route for accessing allylic azides. Furthermore, the one-pot process consisting of Pd-catalyzed allylic azidation of alkenes and Cu-catalyzed 1,3-dipolar cycloaddition led directly to the 1,2,3-triazole from the alkene. The formed allylic azide can be also in situ reduced to the allylic amine or oxidized to the alkenyl nitrile. the Partner Organisations 2014.
Nickel-catalyzed reductive allylation of aryl bromides with allylic acetates
Cui, Xiaozhan,Wang, Shulin,Zhang, Yuwei,Deng, Wei,Qian, Qun,Gong, Hegui
supporting information, p. 3094 - 3097 (2013/05/23)
This paper highlights Ni-catalyzed allylation of electron-rich aryl bromides with a variety of substituted allylic carbonates using zinc as the terminal reductant, affording E-alkenes regioselectively in good to excellent yields by the addition of aryl to the less hindered allylic carbon. The electron-deficient aryl bromides and chlorides are also highly efficient coupling partners. The Royal Society of Chemistry 2013.
Acetalization allows the photoheterolysis of the Ar-Cl bond in chlorobenzaldehydes and chloroacetophenones
Raviola, Carlotta,Protti, Stefano,Ravelli, Davide,Mella, Mariella,Albini, Angelo,Fagnoni, Maurizio
supporting information, p. 9094 - 9101 (2013/01/15)
The nonaccessibility of phenyl cations by irradiation of electron-poor aryl chlorides was circumvented by transforming the carbonyl group of aromatic ketones or aldehydes into the corresponding 1,3-dioxolanes and the carboxyl group of benzoate ester into
Facile synthesis of aryl(het)cyclopropane catalyzed by palladacycle
Zhang, Min,Cui, Xiuling,Chen, Xiaopei,Wang, Lianhui,Li, Jingya,Wu, Yusheng,Hou, Lifen,Wu, Yangjie
experimental part, p. 900 - 905 (2012/02/01)
Sphos (2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′- biphenyl) adduct of cyclopalladated ferrocenylimine (IIe) exhibited highly catalytic activity for the Suzuki cross-coupling reaction of cyclopropylboronic acid with aryl(het) halides with 1 mol % catalyst loading. This process was applied to both of aryl and heteroaryl halides (Br and Cl), and made the various arylcyclopropane and heteroarylcyclopropane to be easily synthesized. A variety of substituents on the aryl halides, such as alkyl, acetyl, benzoyl, ether, formyl, carboxylate, methoxy, nitro and cyano were tolerated.
Palladium-catalyzed allyl cross-coupling reactions with in situ generated organoindium reagents
Lee, Kooyeon,Kim, Hyunseok,Mo, Juntae,Lee, Phil Ho
scheme or table, p. 2147 - 2157 (2011/10/31)
Inter- and intramolecular palladium-catalyzed allyl cross-coupling reactions, using allylindium generated in situ from allyl halides and indium, is demonstrated. Allylindium compounds may be effective nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions. A variety of allyl halides, such as allyl iodide, allyl bromide, crotyl bromide, prenyl bromide, geranyl bromide, and 3-bromocyclohexene afforded the allylic cross-coupling products in good to excellent yields. Stereochemistry of the double bond is retained in the allylic cross-coupling reactions. Electrophilic cross-coupling partners, such as aryl and vinyl halides, dibromoolefin, alkynyl iodide, and aryl and vinyl triflates participate in these reactions. The presence of various substituents, such as n-butyl, ketal, acetyl, ethoxycarbonyl, nitrile, N-phenylamido, nitro, and chloride groups on the aromatic ring of electrophilic coupling partners showed little effect on the efficiency of the reactions. The present conditions work equally well for not only intermolecular but also intramolecular palladium-catalyzed cross-coupling reactions. These methods provide an efficient synthetic method for the introduction of an allyl group, which can be easily further functionalized to afford an sp2- and sp-hybridized carbon. The present method complements existing synthetic methods as a result of advantageous features such as easy preparation and handling, thermal stability, high reactivity and selectivity, operational simplicity, and low toxicity of allylindium reagents.
