Copper-catalyzed ortho-halogenation of protected anilines

Urones, Beatriz; Martínez, Ángel Manu; Rodríguez, Nuria; Arrayás, Ramón Goméz; Carretero, Juan C.

doi:10.1039/c3cc47174h

Cited by 95 publications

(35 citation statements)

References 47 publications

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“…[47] In their process,ascreening of protecting groups revealed that the NH(SO 2 Py) group was uniquely effective for the high monoselectivity andr egioselectivity. This method uses convenient halogen sources, N-halosuccinimides (NXS,X= Cl, Br), providing an interesting procedure for the formation of ortho-Cl and ortho-Br aniline derivatives.…”

Section: C à Pb Ond Formationmentioning

confidence: 99%

Copper‐Catalyzed or ‐Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups

2016

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Copper salts, which are abundant, relatively inexpensive and possess low toxicity,h ave long been useda sv ersatile catalysts for various reactions in organic synthesis.R ecently,t he development of Cu-catalyzed or -mediated C À Hf unctionalization reactions has gaineds ignificant attention. Since the pioneering work of Daugulis on the introduction of 8-aminoquinoline and picolinic acid auxiliariesa sr emovable directing groups in transitionm etal-catalyzed C À Hb onda ctivations,t he combination of copper saltsw ith these bidentated irecting groups has emerged as an innovatives trategyf or the construction of carbon-carbon or carbon-heteroatom bonds through C À Hb ond cleavage.I na ddition to the 8-aminoquinoline and picolinamides ystems,s everal other bidentate directing groups including the 2-aminophenyloxazoline group by Yu andD ai andt he PIP systemb yS hi, have been developeda sw ell. This review intends to cover most of the recent advances on copper-catalyzed or -mediatedd irect sp 2 and sp 3 C À Hb ondf unctionalizations assisted by these bidentate directing groups.T he major achievements in this area are discussed and catalogued by the type of bonds formed (C À C, C À O, C À N, C À S, C À Pe tc.). Special attention is paid to the reaction mechanisms.S electede xamples of substrates are listed as well. In addition, apersonal outlook is given at the end.1I ntroduction 2C À CB ond Formation 3C À OB ond Formation 4C À NBond Formation 5C À SBond Formation 6C À PBondF ormation 7C À X(X= F, Cl, Br,I )BondF ormation 8I ntermolecularC À HA ctivation-Cyclization Tandem Reactions 9S ummary andOutlook

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Section: C à Pb Ond Formationmentioning

confidence: 99%

Copper‐Catalyzed or ‐Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups

2016

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“…67 Ortho-mono-halogenation of anilines could be achieved with CuX 2 -NXS (X = Cl, Br)system. The one-step removal of the 2-pyridylsulfonyl auxiliary under mild reductive conditions afforded the free primary amine in high yield.…”

Section: Carbon-halogen Bond Formationmentioning

confidence: 99%

Recent advances in copper-mediated chelation-assisted functionalization of unactivated C–H bonds

2016

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Transition metal-catalyzed direct functionalization of C-H bonds has recently emerged as a powerful strategy for the construction of carbon-carbon and carbon-heteroatom bonds. Among various metals employed, base metal copper has attracted significant attention owing to its relatively low cost, abundance, and versatile reactivity. This review aims to comprehensively summarize the recent advances in copper-mediated (both stoichiometric and catalytic) chelation-assisted functionalization of unactivated C-H bonds.Scheme 1 Copper-mediated cross-coupling and C-H functionalization.

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“…Inspired by the report on copper‐catalyzed functionalization of C(sp 2 )H bonds by the group of Yu,3 Daugulis and co‐workers reported the first example of copper‐promoted bidentate ligand‐directed CH functionalization reactions on sp 2 carbons in 2012: the sulfenylation of benzoic acid and benzylamine derivatives 4. Following this discovery, copper‐catalyzed direct amination,5 amidation,5b arylation,6 chlorination,7 etherification,8 and fluorination9 of arenes were rapidly established. Mechanistically, either an organometallic CH activation/functionalization or a single‐electron‐transfer pathway is believed to be involved in the process 5b.…”

Section: Optimization Of Reaction Conditions[a]mentioning

confidence: 99%

Copper‐Promoted Site‐Selective Acyloxylation of Unactivated C(sp³)H Bonds

Zhao

2014

Chemistry An Asian Journal

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Copper-catalyzed ortho-halogenation of protected anilines

Abstract: A practical Cu-catalyzed direct ortho-halogenation of anilines under aerobic conditions has been developed. The reaction shows typically excellent mono-substitution selectivity, high ortho-regiocontrol and large functional group tolerance.

Cited by 95 publications

References 47 publications

Copper‐Catalyzed or ‐Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups

Copper‐Catalyzed or ‐Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups

Recent advances in copper-mediated chelation-assisted functionalization of unactivated C–H bonds

Copper‐Promoted Site‐Selective Acyloxylation of Unactivated C(sp³)H Bonds

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Copper-catalyzed ortho-halogenation of protected anilines

Abstract: A practical Cu-catalyzed direct ortho-halogenation of anilines under aerobic conditions has been developed. The reaction shows typically excellent mono-substitution selectivity, high ortho-regiocontrol and large functional group tolerance.

Cited by 95 publications

References 47 publications

Copper‐Catalyzed or ‐Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups

Copper‐Catalyzed or ‐Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups

Recent advances in copper-mediated chelation-assisted functionalization of unactivated C–H bonds

Copper‐Promoted Site‐Selective Acyloxylation of Unactivated C(sp3)H Bonds

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Copper‐Promoted Site‐Selective Acyloxylation of Unactivated C(sp³)H Bonds