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N-HETEROCYCLIC CARBENES: From Laboratory Curiosities to Efficient Synthetic Tools

Second Edition  

Silvia Díez-González, Editor

RSC Catalysis Series, 2016

In less than 20 years N-heterocyclic carbenes (NHCs) have become well-established ancillary ligands for the preparation of transition metal-based catalysts. This is mainly due to the fact that NHCs tend to bind strongly to metal centres, avoiding the need of excess ligand in catalytic reactions. Also, NHC‒metal complexes are often insensitive to air and moisture, and have proven remarkably resistant to oxidation. This book showcases the wide variety of applications of NHCs in different chemistry fields beyond being simple phosphine mimics. This second edition has been updated throughout, and now includes a new chapter on NHC‒main group element complexes. It covers the synthesis of NHC ligands and their corresponding metal complexes, as well as their bonding and stereoelectronic properties and applications in catalysis. This is complemented by related topics such as organocatalysis and biologically active complexes. Written for organic and inorganic chemists, this book is ideal for postgraduates, researchers and industrialists.

 For the first edition of this volume, see: RSC Catalysis Series, 2010

Recent publications


19. Copper-mediated reduction of azides under seemingly oxidising conditions: Catalytic and computational studies

red azides

 

Zelenay, B.; Besora, M.; Monasterio, Z.; Ventura-Espinosa, D.; White, A. J.; Maseras, F.; Díez-González, S.

Catal. Sci Tech.  2018, 8, 5763–5773

The reduction of aryl azides in the absence of an obvious reducing agent is reported. Careful catalyst design led to the production of anilines in the presence of water and air. The reaction medium (toluene/water) is crucial for the success of the reaction, as DFT calculations support the formation of benzyl alcohol as the oxidation product. A singular catalytic cycle is presented for this transformation based on four key steps: nitrene formation through nitrogen extrusion, formal oxidative addition of water, C(sp3)–H activation of toluene and reductive elimination.


18. The acetate proton shuttle between mutually trans ligands

De Aguirre, A.; Díez-González, S.; Maseras, F.; Martín, M.; Sola, E. om maseras ru

Organometallics, 2018, 37, 2645–2651

This work addresses a counterintuitive observation in the reactivity of the well-known ruthenium complexes [Ru(X)H(CO)(PiPr3)2], according to which the 5-coordinate chloro complex (X = Cl, 1) is less reactive toward phenylacetylene than its 6-coordinate acetate analogue (X = κO2-OC(O)Me, 3), since 3 undergoes a hydride-to-alkenyl-to-alkynyl transformation, whereas the reaction of 1 stops at the alkenyl derivative. The experimental kinetics of the key alkenyl-to-alkynyl step in the acetate complex are compared to the results of DFT calculations, which disclose the ability of the acetate not only to assist the alkyne C–H activation step via a CMD mechanism but also to subsequently deliver the proton to the alkenyl ligand. Possible consequences of this mechanistic resource connecting mutually trans ligands are briefly discussed on the basis of reported chemoselectivity changes induced by carboxylate ligands in 1-alkyne hydrosilylations catalyzed by this type of ruthenium complexes.

 


17. Thermal azide-alkene cycloaddition reactions: Straightforward multi-gram access to Δ2-1,2,3-triazolines in deep eutectic solvents

Sebest, F.; Casarrubios, L.; Rzepa, H. S.; White, A. J. P.; Díez-González, S.

Green Chem

Green Chem. 2018, 20, 4023–4035

The multi-gram synthesis of a wide range of 1,2,3-triazolines via azide–alkene cycloaddition reactions in a Deep Eutectic Solvent (DES) is reported. The role of DES in this transformation as well as the origin of the full product distribution was studied with an experimental/computational-DFT approach.

 


16. Ring-expanded N-heterocyclic carbenes for copper-mediated azide-alkyne Click cycloaddition reactions

toc

Sebest, F.; Dunsford, J. J.; Adams, M.; Pivot, J.; Newman, P. D.; Díez-González, S.

ChemCatChem 2018, doi: 10.1002/cctc.201701992

In this article we studied different copper(I) complexes bearing ring‐expanded N‐heterocyclic carbene ligands in the azide–alkyne cycloaddition reaction. We showed that the six‐membered NHC ligands outperform well‐established five‐membered ones and [CuI(Mes‐6)] displayed a remarkable catalytic activity while respecting the strict criteria for click reactions.


15. Homo- and heteroleptic copper(I) complexes with diazabutadiene ligands: Synthesis, solution- and solid-state structural studies

toc

Zelenay, B.; Frutos-Pedreño, R.; Markalain-Barta, J.; Vega-Isa, E.; White, A. J. P.; Díez-González, S.

Eur. J. Inorg. Chem. 2016, 4649–4658

Herein we report the synthesis of several complexes with diazabutadiene complexes: [Cu(DABR)2]BF4), [Cu(DABR)(NCMe)2]BF4 and [CuCl(DABR)]. These complexes, which remain scarce in the literature are air-stable and their behaviour both in the solid state as well as in solution was studied by means of X‐ray crystallography, NMR and UV/Vis spectroscopy.


14. Functionalised [(NHC)Pd(allyl)Cl] complexes: Synthesis, immobilisation and application in cross-coupling and dehalogenation reactions

toc

Collinson, J.-M.; Wilton-Ely, J. D. E. T.; Díez-González, S.

Catal. Commun. 2016, 87, 78–81

A novel NHC–palladium(II) complex and its immobilised version were prepared and fapplied in Suzuki-Miyaura cross coupling and chloroarene dehalogenation reactions. Also, an unexpected palladium-mediated transfer hydrogenation of a carbonyl compound was evidenced.


13. Copper(I)‒phosphinite complexes in Click chemistry : Three component reactions and preparation of 5-iodotriazoles

toc

Pérez, J. M.; Crosbie, P.; Lal, S.; Díez-González, S.

ChemCatChem 2016, 8, 2222–2226

The remarkable activity displayed by copper(I)–phosphinite complexes of general formula [CuBr(L)] in two challenging cycloadditions is reported: a) the one‐pot azidonation/cycloaddition of boronic acids, NaN3, and terminal alkynes; b) the cycloaddition of azides and iodoalkynes. These air‐stable catalysts led to very good results in both cases and the expected triazoles could be isolated in pure form under ‘Click‐suitable’ conditions.


12. HBF4-Catalysed nucleophilic substitutions of propargylic alcohols

Barreiro, E.; Sanz-Vidal, A.; Tan, E.; Lau, S.-H.; Sheppard, T. D.; Díez-González, S.

'HBF4-Catalysed Nucleophilic Substitutions of Propargylic Alcohols'

Eur. J. Org. Chem. 2015, 7544-7549

The activity of HBF4 (aqueous solution) as a catalyst in propargylation reactions is presented. Diverse types of nucleophiles were employed in order to form new C–O, C–N and C–C bonds in technical acetone and in air. Good to excellent yields and good chemoselectivities were obtained using low acid loading (typically 1 mol‐%) under simple reaction conditions.


11. Catalytic and mechanistic studies of N-heterocyclic carbene or phosphine-containing copper(I) complexes for the synthesis of 5-iodo-1,2,3-triazoles

'Catalytic and mechanistic studies of N-heterocyclic carbene or phosphine-containing copper(I) complexes for the synthesis of 5-iodo-1,2,3-triazoles'

Lal, S.; Rzepa, H. S.; Díez-González, S.

ACS Catalysis 2014, 4, 2274-2287

 Two complementary catalytic systems are reported for the 1,3-dipolar cycloaddition of azides and iodoalkynes. These are based on two commercially available/readily available copper complexes, [CuCl(IPr)] or [CuI(PPh3)3], which are active at low metal loadings (PPh3 system) or in the absence of any other additive (IPr system). These systems were used for the first reported mechanistic studies on this particular reaction. An experimental/computational-DFT approach allowed to establish that (1) some iodoalkynes might be prone to dehalogenation under copper catalysis conditions and, more importantly, (2) two distinct mechanistic pathways are likely to be competitive with these catalysts, either through a copper(III) metallacycle or via direct π-activation of the starting iodoalkyne.


10. Chiral transition-metal complexes as Brønsted-acid catalysts for the asymmetric Friedel-Crafts hydroalkoxylation of indoles

Carmona, D.; Lamata, M. P.; Sánchez, A. Viguri, F.; Rodríguez, R.; Oro, L. A.; Liu, C.; Díez-González, S.; Maseras, F. 

10. Carmona, D.; Lamata, M. P.; Sánchez, A. Viguri, F.; Rodríguez, R.; Oro, L. A.; Liu, C.; Díez-González, S.; Maseras, F.

Dalton Trans. 2014, 43, 11260-11268

The Friedel–Crafts reaction between 3,3,3-trifluoropyruvates and indoles is efficiently catalysed by the iridium complex [(η5-C5Me5)Ir{(R)-Prophos}(H2O)][SbF6]2 (1) with up to 84% ee. Experimental data and theoretical calculations support a mechanism involving the Brønsted-acid activation of the pyruvate carbonyl by the protons of the coordinated water molecule in 1. Water is not dissociated during the process and, therefore, the catalytic reaction occurs with no direct interaction between the substrates and the metal.

This article is part of the themed collection 'Synergy between experimental and theory'

'Chiral transition-metal complexes as Brønsted-acid catalysts for the asymmetric Friedel-Crafts hydroalkoxylation of indoles

 


9. Reusable and highly active supported copper(I)–NHC catalysts for Click chemistry

Collinson, J.-M.; Wilton-Ely, J. D. E. T.; Díez-González, S. toc

Chem. Commun. 2013, 49, 11358-11360

Immobilised [Cu(NHC)] catalysts are reported for the preparation of 1,2,3-triazoles. In addition to showing outstanding catalytic activity, the catalyst systems are easy to prepare and can be recycled many times.

This article is highligted in the back cover of the issue:

Immobilised [Cu(NHC)] catalysts are reported for the Click preparation of 1,2,3-triazoles; these are highly active, easy to prepare and to recycle.


8. Well-defined diimine copper(I) complexes as catalysts in Click azide-alkyne cycloaddition reactions

Markalain-Barta, J.; Díez-González, S. 

Well-defined diimine copper(I) complexes as catalysts in Click azide-alkyne cycloaddition reactions'

Molecules 2013, 18, 8919–8928

[Invited contribution to special issue on 'Advances in Click Chemistry']

A series of 1,4-disubstituted 1,2,3-triazoles have been prepared in high yields while respecting the stringent Click criteria. In these reactions, highly stable pre-formed complexes bearing diimine ligands were used.


7. On the unique reactivity of Pd(OAc)2 with organic azides: Expedient synthesis of nitriles and imines

TOC

Martínez-Sarti, L.; Díez-González, S.

ChemCatChem 2013, 5, 1722–1724

Pd(OAc)2 can oxidise primary azides into their corresponding nitriles or imines under simple, technical conditions. This very user-friendly system also displays complementary selectivity to that of previously reported systems.


6. Synthesis of 1,3-bis(2,4,6-trimethylphenyl)imidazolium salts: SIMes∙HBr, SIMeS∙HBF4 and SIMes∙HPF6

Gautier, A.; Cisnetti, F.; Díez-González, S.; Gibard C. 

 Protocols Exchange 2012, doi:10.1038/protex.2012.048

N,N’–bis–(2,4,6–trimethylphenylamino)ethane dihydrobromide is obtained in a single step through the dialkylation of dibromoethane. It serves as a versatile starting material for the synthesis of imidazolium salts: SIMes.HBr, SIMes.HCl, SIMes.HPF6 and SIMes.HBF4.