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FLP-Mediated C–H-Activation

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Frustrated Lewis Pairs

Part of the book series: Molecular Catalysis ((MOLCAT,volume 2))

Abstract

The C–H functionalization of aromatic molecules is a green approach that allows creating complex molecules from simple reagents. While these transformations are mainly catalysed using transition metal complexes, the main group molecules, including frustrated Lewis pairs, have been shown to be efficient species to functionalize C–H bonds. This chapter describes the different approaches and mechanisms that are used to activate C–H bonds using Lewis acidic boron and silicon species. On the one hand, highly electrophilic cationic boron and silicon species can activate C–H bonds by an electrophilic addition pathway that generates a Wheland intermediate that is further deprotonated by a Lewis base. On the other hand, frustrated Lewis pairs act in a concerted way where the Lewis acid activation and the deprotonation by a base occur simultaneously. In both systems, the nature of the Lewis acid and Lewis base plays an important role on the activity and the selectivity of the functionalization reaction.

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Abbreviations

HBPin:

4,4,5,5-Tetramethyl-1,3,2-dioxaborolane

HBCat:

Catecholborane

Pin:

Pinacolate

Cat:

Catecholate

9-BBN:

9-Borabicyclo[3.3.1]nonane

3c-2e:

Three-centre two-electron

AIBN:

Azobisisobutyronitrile

Ar:

Aryl-

Bn:

Benzyl-

BOC:

tert-Butyloxycarbonyl

bpy:

2,2′-Bipyridine

COD:

1,5-Cyclooctadiene

Cy:

Cyclohexyl-

DMF:

Dimethylformamide

DMSO:

Dimethyl sulfoxide

DTBMP:

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

dTBP:

2,6-Di-tert-butylpyridine

EAS:

Electrophilic aromatic substitution

Et:

Ethyl-

exp:

Experimental

FDA:

Food and Drug Administration

FLP:

Frustrated Lewis pair

fur:

Furyl-

HOMO:

Highest occupied molecular orbital

Int:

Intermediate

LUMO:

Lowest unoccupied molecular orbital

m :

meta-

Me:

Methyl-

NMR:

Nuclear magnetic resonance

NTf2−:

Bistriflimide anion, [(CF3SO2)2N]−

o :

Ortho-

p :

Para-

PAH:

Polycyclic aromatic hydrocarbons

Ph:

Phenyl-

PMP:

1,2,2,6,6-Pentamethylpiperidine

Pip:

Piperidyl-

tBu:

Tert-Butyl-

TfO− :

Triflate anion, (CF3SO3−)

THF:

Tetrahydrofuran

THT:

Tetrahydrothiophene

TIPS:

Triisopropylsilyl-

TM:

Transition metal

TMP:

2,2,6,6-Tetramethylpiperidine

TMS:

Trimethylsilyl

Tol:

Tolyl-

Ts:

Tosyl-

TS:

Transition state

tTBP:

2,4,6-Tri-tert-butylpyridine

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  1. Département de Chimie, Université Laval, 1045 Avenue de la Médecine, Québec City, Québec, G1V 0A6, Canada

    Yashar Soltani & Frédéric-Georges Fontaine

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  1. Yashar Soltani
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  2. Frédéric-Georges Fontaine
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Correspondence to Frédéric-Georges Fontaine .

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  1. Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam, The Netherlands

    J. Chris Slootweg

  2. School of Chemistry, University of Birmingham, Edgbaston, UK

    Andrew R. Jupp

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Soltani, Y., Fontaine, FG. (2021). FLP-Mediated C–H-Activation. In: Chris Slootweg, J., Jupp, A.R. (eds) Frustrated Lewis Pairs. Molecular Catalysis, vol 2. Springer, Cham. https://doi.org/10.1007/978-3-030-58888-5_4

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