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meta- and para-Selective C–H Functionalization by C–H Activation

  • Jie Li
  • Suman De Sarkar
  • Lutz Ackermann
Part of the Topics in Organometallic Chemistry book series (TOPORGAN, volume 55)

Abstract

Transition metal-catalyzed C–H bond functionalization has recently emerged as an indispensable tool for transforming otherwise unreactive C–H bonds. In addition to various strategies for ortho-selective functionalization via chelation assistance, organometallic C–H activation has recently enabled novel functionalizations of (hetero)arenes at remote meta- or para-positions. The meta- and para-selectivity was governed either by the inherent substrate structure or by the transition metal catalyst. Herein we summarize the rapid recent progress in meta- and para-selective aromatic C–H functionalization until May 2015.

Keywords

C–H activation Chelation Remote functionalization Selectivity Transition metal catalysis 

Abbreviations

Ac

Acetyl

Ar

Aryl

AMLA

Ambiphilic metal-ligand activation

Bn

Benzyl

Bu

Butyl

BQ

1,4-Benzoquinone

cat

Catalytic

cod

1,4-Cyclooctadienyl

Cp*

Pentamethylcyclopentadienyl

Cy

Cyclohexyl

CMD

Concerted metalation deprotonation

dppb

1,4-Bis(diphenylphosphino)butane

dppe

1,2-Bis(diphenylphosphino)ethane

dtbpy

4,4′-Di-tert-butyl-2,2′-dipyridyl

DCE

1,2-Dichloroethane

DG

Directing group

DMF

N,N-Dimethylformamide

DMPU

1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone

equiv.

Equivalent

E

Electrophile

EDG

Electron-donating group

EWG

Electron-withdrawing group

FG

Functional group

Gly

Glycine

Hal

Halogen

Het

Heteroatom

HBCat

Catecholborane

HFIP

Hexafluoroisopropanol

Ind

Indenyl

KIE

Kinetic isotope effect

L

Ligand

m

meta

M

Metal

Me

Methyl

Mes

Mesityl

MPAA

Mono-N-protected amino acid

MTBE

Methyl tert-butyl ether

NMP

N-Methylpyrrolidinone

o

ortho

p

para

Ph

Phenyl

Pin

Pinacol

Piv

Pivaloyl

Pr

Propyl

PEPPSI

[1,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride

T

Template

TBA

Tetrabutylammonium

TBP

Tributyl phosphate

TFA

Trifluoroacetic acid

TM

Transition metal

TMP

2,2,6,6-Tetramethylpiperamidyl

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Copyright information

© Springer International Publishing Switzerland 2015

Authors and Affiliations

  1. 1.Institut für Organische und Biomolekulare ChemieGeorg-August-Universität GöttingenGöttingenGermany

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