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Functionalization of Aromatic N-Heterocycles with C(sp3)–H Sources via CDC Reactions

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Heterocycles via Cross Dehydrogenative Coupling

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Abstract

Nitrogen-containing heterocycles are a ubiquitous nature and synthetic compounds having wide spectrum of activities, which has found applications in various industrial fields. Among a variety of synthetic approaches toward substituted N-heterocycles, C(sp2)–H functionalization represents the most rapid and convenient transformation. In this review, we concentrated attention on the methods of construction of new C–C bonds via direct coupling of N-heterocyclic C(sp2)–H with C(sp3)–H derivatives, which is called cross-dehydrogenative coupling and satisfied the requirements of “atom economy” and “green chemistry.” Alkanes, ethers, amines and amides, methylarenes, etc., were involved in the oxidative process with N-heterocyclic compound.

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Abbreviations

Ar:

Aryl

BHP:

2,6-Di-tert-butyl-4-methylphenol

Binap:

2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl

BPO:

Benzoyl peroxide

CCHE:

Cross-coupling hydrogen evolution

CDC:

Cross-dehydrogenative coupling

DCDC:

Double cross-dehydrogenative coupling

CFL:

Compact fluorescent lamp

DCE:

1,2-Dichloroethane

DCP:

Dicumyl peroxide

DDQ:

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone

DG:

Directing group

DMA:

N,N-Dimethylacetamide

DMF:

N,N-Dimethylformamide

DTBP:

Di-tert-butyl peroxide

HAT:

Hydrogen atom transfer

LED:

Light-emitting diode

PG:

Protecting group

Ph:

Phenyl

PIFA:

Phenyliodine bis-(trifluoroacetate)

PMP:

p-Methoxyphenyl

Py-GC-MS:

Pyrolysis–gas chromatography–mass spectrometry

RT:

Room temperature

SET:

Single-electron transfer

TBAB:

Tetra-n-butylammonium bromide

TBAI:

Tetra-n-butylammonium iodide

TBPB:

Tert-butyl perbenzoate

TEMPO:

(2,2,6,6-Tetramethylpiperidin-1-yl)oxidanyl

TFA:

Trifluoroacetic acid

THF:

Tetrahydrofuran

THIQ:

Tetrahydroisoquinoline

TMU:

N,N,N′,N′-tetramethylurea

Tol:

Tolyl

TsOH:

p-Toluenesulfonic acid

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Acknowledgments

This work was supported by the Russian Science Foundation (project #18-13-00365).

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Authors and Affiliations

  1. Ural Federal University, Mira 19, 620002, Ekaterinburg, Russian Federation

    Ramil F. Fatykhov, Igor A. Khalymbadzha & Oleg N. Chupakhin

  2. I. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, S. Kovalevskaya/Akademicheskaya, 22/20, 620219, Ekaterinburg, Russian Federation

    Igor A. Khalymbadzha & Oleg N. Chupakhin

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  1. Ramil F. Fatykhov
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  3. Oleg N. Chupakhin
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Correspondence to Igor A. Khalymbadzha .

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Editors and Affiliations

  1. National Institute of Pharmaceutical Education and Research, Guwahati, Assam, India

    Ananya Srivastava

  2. Indian Institute of Technology Guwahati, Guwahati, Assam, India

    Chandan K. Jana

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Fatykhov, R.F., Khalymbadzha, I.A., Chupakhin, O.N. (2019). Functionalization of Aromatic N-Heterocycles with C(sp3)–H Sources via CDC Reactions. In: Srivastava, A., Jana, C. (eds) Heterocycles via Cross Dehydrogenative Coupling. Springer, Singapore. https://doi.org/10.1007/978-981-13-9144-6_1

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