<i>Ortho vs Ipso</i>: Site-Selective Pd and Norbornene-Catalyzed Arene C–H Amination Using Aryl Halides

Dong, Zhe; Dong, Guangbin

doi:10.1021/ja410823e

Cited by 296 publications

(146 citation statements)

References 89 publications

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“…[16] Whereas ortho-selective C À Hf unctionalization reactions of arenes have been well developed, meta-selective CÀHf unctionalization remains ac hallenge. [19] As eparate approach using Pd II /NBE cooperative catalysis was developed by the groups of Yu,Dong, Zhao,Shi, Ferreira, and others, [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] who drew inspiration from the Catellani reaction. [19] As eparate approach using Pd II /NBE cooperative catalysis was developed by the groups of Yu,Dong, Zhao,Shi, Ferreira, and others, [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] who drew inspiration from the Catellani reaction.…”

Section: Meta-selective C à Hf Unctionalization Of Arenesmentioning

confidence: 99%

Palladium(II)‐Initiated Catellani‐Type Reactions

Cheng

Chen

et al. 2019

Angewandte Chemie

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Scheme 3. Selective C2 alkylation of NH-indoles. DMA = N,N-dimethylacetamide, DMF = N,N-dimethylformamide. Scheme 4. a) Control experiments and isolated intermediates. b) Proposed catalytic cycle for the Pd II /NBE-catalyzed C2 alkylationo fNHindoles. Scheme 5. C2 alkylation of an NH-tryptophan derivative. Scheme 6. C2 trifluoroethylation of NH-indoles. acac = acetylacetonate, dbm = dibenzoylmethane. Angewandte Chemie Kurzaufsätze 5893 Scheme 10. Proposed catalytic cycle of the Pd II /NBE-co-catalyzed meta CÀHfunctionalization.Scheme 11. meta-SelectiveC ÀHa lkylations. Angewandte ChemieKurzaufsätze 5895 Scheme 15. meta-SelectiveC ÀHa rylation of nosyl-protected aryl ethylamines, phenylglycines, and 2-aryl anilines.Scheme 16. meta-Selective CÀHa rylation of benzyl sulfonamides.Scheme 17. meta-Selective CÀHarylation of benzyl amines.Scheme 18. meta-Selective CÀHa rylation of aniline, heterocyclic aromatic amine, phenol, and 2-benzylh eterocycle derivatives.Scheme 19. meta-Selective CÀHa rylation of benzylamine derivatives.Scheme 24. meta-Selective CÀHa minationo fa niline, phenol, benzylamine derivatives and masked aromatic aldehydes.Scheme 25. meta-Selective CÀHa lkynylation of aniline derivatives.Scheme 26. Enantioselective meta CÀHa rylation and alkylation.

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Section: Meta-selective C à Hf Unctionalization Of Arenesmentioning

confidence: 99%

Palladium(II)‐Initiated Catellani‐Type Reactions

Cheng

Chen

et al. 2019

Angewandte Chemie

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“…110 The authors utilized a reductive Catellani reaction pathway to install an amino group ortho to the position previously occupied by the halogen. Numerous (hetero)arene examples are provided, including three quinolines.…”

Section: C5/c6/c7–h-functionalizationmentioning

confidence: 99%

Recent advances in the C–H-functionalization of the distal positions in pyridines and quinolines

2015

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This review summarizes recent developments in the C–H-functionalization of the distal positions of pyridines, quinolines and related azaheterocycles. While the functionalization of the C2 position has been known for a long time and is facilitated by the proximity to N1, regioselective reactions in the distal positions are more difficult to achieve and have only emerged in the last decade. Recent advances in the transition metal-catalyzed distal C–H-functionalization of these synthetically-important azaheterocycles are discussed in detail, with the focus on the scope, site-selectivity and mechanistic aspects of the reactions.

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“…1b), 18–22 we hypothesized that ortho -palladacycle I (Fig. 1c) could react with norbornene to provide an intermediate that can undergo activation of the meta -C–H bond (intermediate II ).…”

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confidence: 99%

Ligand-enabled meta-C–H activation using a transient mediator

Wang

Gong

Fang

et al. 2015

Nature

527

202

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Achieving site selectivity in C–H functionalization reactions is a significant challenge, especially when the target C–H bond is distant from existing functional groups.1–5 Coordination of a functional group to a metal catalyst is often a key driving force and control element in many important reactions including asymmetric hydrogenation,6 epoxidation7, 8, and lithiation9. Exploitation of this effect has led to the development of a broad range of directed C–H activation reactions.10–14 However, such C–H activation methods are limited to proximal C–H bonds, which are spatially and geometrically accessible from the directing functional group. Development of meta-selective C–H functionalizations remains a significant challenge.1–5,15–17 We recently developed a U- shaped template that can be used to overcome this constraint and have shown that it can be used to selectively activate remote meta-C–H bonds.1, 2 While this approach has proven applicable for a diverse set of substrates and catalytic transformations,3–5 the need for a covalently attached complex template is a significant drawback for synthetic applications. In this manuscript, we report an alternative approach, one that employs norbornene as a transient mediator to achieve meta-selective C–H activation with a simple and common ortho-directing group. The use of a newly developed pyridine-based ligand is crucial for relaying the palladium catalyst to the meta position by norbornene following initial ortho- C–H activation. Thus, this catalytic reaction demonstrates the feasibility of switching ortho-selectivity to meta-selectivity in C–H activation of the same substrate by catalyst control.

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Ortho vs Ipso: Site-Selective Pd and Norbornene-Catalyzed Arene C–H Amination Using Aryl Halides

Cited by 296 publications

References 89 publications

Palladium(II)‐Initiated Catellani‐Type Reactions

Palladium(II)‐Initiated Catellani‐Type Reactions

Recent advances in the C–H-functionalization of the distal positions in pyridines and quinolines

Ligand-enabled meta-C–H activation using a transient mediator

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