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Ruthenium in Catalysis pp 81–118Cite as

Ruthenium-Catalyzed Amide-Bond Formation

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Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 48))

Abstract

The amide functionality is one of the most important functional groups in organic and biological chemistry. Classical synthetic strategies of amides involve the stoichiometric, and poor atom efficient, reaction of amines with carboxylic acid derivatives. Transition-metal-catalyzed reactions have emerged in recent years as more atom-economical and powerful tools for preparing amides, opening previously unavailable routes from substrates other than the carboxylic acids and their derivatives. Ruthenium-based catalysts have been at the heart of these advances, and this chapter pretends to give an overview of the field. Among others, the following ruthenium-catalyzed synthetic approaches of amides will be discussed: the hydration of nitriles, the hydrolytic amidation of nitriles with amines, the rearrangement of aldoximes, the coupling of aldehydes with hydroxylamine, and the dehydrogenative amidation of alcohols, aldehydes, and esters.

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Abbreviations

Ac:

Acetyl

acac:

Acetylacetonate

Bn:

Benzyl

cod:

1,5-Cyclooctadiene

cot:

1,3,5,7-Cyclooctatetraene

Cy:

Cyclohexyl

Da:

Dalton

DCE:

1,2-Dichloroethane

DFT:

Density functional theory

DME:

1,2-Dimethoxyethane

DMSO:

Dimethyl sulfoxide

DNA:

Deoxyribonucleic acid

dppb:

1,4-Bis(diphenylphosphino)butane

dppe:

1,2-Bis(diphenylphosphino)ethane

dppm:

Bis(diphenylphosphino)methane

equiv.:

Equivalent(s)

Et:

Ethyl

h:

Hour(s)

i-Bu:

iso-Butyl

IiPr:

1,3-Diisopropylimidazol-2-ylidene

i-Pr:

iso-Propyl

Me:

Methyl

min:

Minute(s)

mol:

Mole(s)

Ms:

Mesyl, methanesulfonyl

MW:

Microwave

n-Bu:

Butyl

NHC:

N-heterocyclic carbene

NSAIDs:

Non-steroidal anti-inflammatory drugs

PCyp3 :

Tricyclopentylphosphine

Pent:

Pentyl

Ph:

Phenyl

PPh2(py-4-NMe2):

2-Diphenylphosphino-4-pyridyl(dimethyl)amine

PPh2py:

2-(Diphenylphosphino)pyridine

Pr:

Propyl

PTA:

1,3,5-Triaza-7-phosphaadamantane

PVP:

Polyvinylpyrrolidone

py:

Pyridine

rt:

Room temperature

s-Bu:

sec-Butyl

t-Bu:

tert-Butyl

terpy:

2,2′:6′,2″-Terpyridine

TOF:

Turnover frequency

TON:

Turnover number

Tp:

Hydrotris(pyrazolyl)borate

Ts:

Tosyl, 4-toluenesulfonyl

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Acknowledgments

Our research in the field of amide-bond forming reactions was supported by MINECO of Spain (projects CTQ2006-08485/BQU, CTQ2010-14796/BQU and CSD2007-00006). We heartily wish to thank our co-workers Dr. Javier Francos and Dr. Rocío García-Álvarez for their strong commitment to this chemistry.

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  1. Laboratorio de Compuestos Organometálicos y Catálisis (Unidad Asociada al CSIC), Red ORFEO-CINQA – Centro de Innovación en Química Avanzada, Departamento de Química Orgánica e Inorgánica, Facultad de Química, Instituto Universitario de Química Organometálica “Enrique Moles”, Universidad de Oviedo, Julián Clavería 8, 33006, Oviedo, Spain

    Pascale Crochet & Victorio Cadierno

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  1. Pascale Crochet
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  2. Victorio Cadierno
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Correspondence to Victorio Cadierno .

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  1. Inst. des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université Rennes1, Rennes, France

    Pierre H. Dixneuf

  2. Inst. des Sciences Chimiques de Rennes, UMR 6226-CNRS-Université de Rennes1, Rennes, France

    Christian Bruneau

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Crochet, P., Cadierno, V. (2014). Ruthenium-Catalyzed Amide-Bond Formation. In: Dixneuf, P., Bruneau, C. (eds) Ruthenium in Catalysis. Topics in Organometallic Chemistry, vol 48. Springer, Cham. https://doi.org/10.1007/3418_2014_78

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