Cu(II)-Mediated C(sp<sup>2</sup>)–H Hydroxylation

Sun, Shang‐Zheng; Shang, Maoyu; Wang, Hongli; Lin, Haixia; Dai, Hui‐Xiong; Yu, Jin‐Quan

doi:10.1021/acs.joc.5b01351

Cited by 91 publications

(61 citation statements)

References 70 publications

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“…In 2006, Yu and co‐workers reported the first example of copper(II)‐catalyzed ortho ‐hydroxylation of phenyl pyridines using molecular oxygen as the oxidant . Yu, Dai, Lin and co‐workers developed a method for the ortho ‐hydroxylation of benzamide derivatives in which the C−H functionalization is directed by a bidentate oxazolyamide group . Koley and co‐workers discovered a copper(I)‐catalyzed acyloxylation of indoline with benzoic acid coupling partners using O 2 as an oxidant.…”

Section: Methodsmentioning

confidence: 99%

“…[9] Yu, Dai, Lin and co-workers developed a method for the orthohydroxylation of benzamide derivatives in which the C À H functionalization is directed by a bidentate oxazolyamide group. [10] Koley and co-workers [11] discovered a copper(I)catalyzed acyloxylation of indoline with benzoic acid coupling partners using O 2 as an oxidant. Although aliphatic carboxylic acids were also tested as coupling partners, the yields were generally low (35 ∼ 55%).…”

Section: Cu-mediated C7 Acetoxylation Of Indolinesmentioning

confidence: 99%

“…However, the yield decreased to 38% upon further increase of the reaction temperature to 140°C (Table 1, entry 6). Finally, the yield could be significantly improved to 84% when replacing MeCN with DCE as the reaction solvent (Table 1, entry 11), While other solvents, such as THF, 1,4dioxane, DMF and DMSO, displayed no superiority (Table 1, entries 7 ∼10). Considering that the acetoxyl group originated from Cu(OAc) 2 * H 2 O, we conducted the reaction by employing 0.5 equivalents of Cu(OAc) 2 * H 2 O.…”

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confidence: 99%

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Cu‐Mediated C7 Acetoxylation of Indolines

Gao

Tang

et al. 2019

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Transition‐metal‐catalyzed acetoxylation or hydroxylation of arene C−H bonds is regarded as a valuable transformation in organic synthesis for the efficient incorporation of oxygen atoms.[1] This mode of C−H oxidation has received much attention due to the important applications of phenol derivatives in natural products, pharmaceuticals, organic synthesis, metal ligands and materials science. Early discoveries for arene C−H oxidation were generally limited due to poor selectivity, low efficiency and harsh conditions.[3] Strategie that rely coordinating directing groups have enabled the direct oxidation of a specific arene C−H bond with high regioselectivity and efficiency. This methods generally employ palladium (II) or ruthenium (II) catalysts and PhI(OAc)2 or other stoichiometric oxidants under acidic conditions (Scheme , 1a). Methods using other transition metals, such as a rhodium (III) catalyzed ortho‐C−H acetoxylation or hydroxylation, have also been reported.

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Section: Methodsmentioning

confidence: 99%

Section: Cu-mediated C7 Acetoxylation Of Indolinesmentioning

confidence: 99%

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confidence: 99%

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Cu‐Mediated C7 Acetoxylation of Indolines

Gao

Tang

et al. 2019

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“…In 2015, another ortho ‐C–H activation reaction of aromatic amides with amide‐oxazoline as the directing group and Cu(OAc) 2 as the catalyst was designed by Yu's team (Scheme ) . Interestingly, unlike the former reaction, the highlight of this reaction is that O 2 is the sole oxidant rather than air for the ortho ‐hydroxylation of aromatic amides.…”

Section: Ortho‐c–h Functionalization Of Aromatic Amidesmentioning

confidence: 99%

C–H Functionalization of Aromatic Amides

et al. 2020

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Since the beginning of the 21st century, significant progress has been made in transition metal‐catalyzed C–H functionalization of aromatic amides. The achievements in this field have mainly focused on ortho (proximal) functionalization, there have been far fewer reports on remote C–H functionalization, and para‐ and meta‐selective functionalizations remain a major challenge. Interestingly, there are few related comments in this field. In a few published cases, the scope of the report is relatively narrow, either to comment on the functionalization of a specific directing group or to summarize the functionalization of a specific reaction site. Herein, for the first time, we have comprehensively summarized the C–H functionalization of aromatic amides. This review is divided into three parts: ortho‐, para‐ and meta‐C–H functionalization of aromatic amides, and is subdivided according to the type of catalyst. The directing groups, reaction types, conditions, mechanism and applications of the corresponding reactions are discussed in detail.

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“…Thed etailed mechanistic investigations suggested that the reactionm ight go through aC u(OAc) 2 -mediated acetoxylation followed by ar apid hydrolysis.M orer ecently, Yu and co-workers also describedaC u(II)-mediated ortho-C À Hh ydroxylation using 2-aminophenyloxazoline as the directing group (Scheme 15b). [26] In this transformation, the use of O 2 as oxidant and water as additive is crucial for achieving high conversion.…”

Section: C à Ob 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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Cu(II)-Mediated C(sp²)–H Hydroxylation

Abstract: A Cu(II)-mediated ortho-C-H hydroxylation using a removable directing group has been developed. The reaction exhibits considerable functional group tolerance. The use of O2 as an oxidant is crucial for the reactivity. Water is also found to significantly improve this reaction.

Cited by 91 publications

References 70 publications

Cu‐Mediated C7 Acetoxylation of Indolines

Cu‐Mediated C7 Acetoxylation of Indolines

C–H Functionalization of Aromatic Amides

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

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Cu(II)-Mediated C(sp2)–H Hydroxylation

Abstract: A Cu(II)-mediated ortho-C-H hydroxylation using a removable directing group has been developed. The reaction exhibits considerable functional group tolerance. The use of O2 as an oxidant is crucial for the reactivity. Water is also found to significantly improve this reaction.

Cited by 91 publications

References 70 publications

Cu‐Mediated C7 Acetoxylation of Indolines

Cu‐Mediated C7 Acetoxylation of Indolines

C–H Functionalization of Aromatic Amides

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

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Cu(II)-Mediated C(sp²)–H Hydroxylation