N-HETEROCYCLIC CARBENES: From Laboratory Curiosities to Efficient Synthetic Tools
Silvia Díez-González, Editor
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
16. Ring-expanded N-heterocyclic carbenes for copper-mediated azide-alkyne Click cycloaddition reactions
Sebest, F.; Dunsford, J. J.; Adams, M.; Pivot, J.; Newman, P. D.; Díez-González, S.
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
Zelenay, B.; Frutos-Pedreño, R.; Markalain-Barta, J.; Vega-Isa, E.; White, A. J. P.; Díez-González, S.
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
Collinson, J.-M.; Wilton-Ely, J. D. E. T.; Díez-González, S.
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. Pérez, J. M.; Crosbie, P.; Lal, S.; Díez-González, S.
‘Copper(I)‒phosphinite complexes in Click chemistry : Three component reactions and preparation of 5-iodotriazoles’
12. Barreiro, E.; Sanz-Vidal, A.; Tan, E.; Lau, S.-H.; Sheppard, T. D.; Díez-González, S.
'HBF4-Catalysed nucleophilic substitutions of propargylic alcohols'
11. Lal, S.; Rzepa, H. S.; Díez-González, S.
'Catalytic and mechanistic studies of N-heterocyclic carbene or phosphine-containing copper(I) complexes for the synthesis of 5-iodo-1,2,3-triazoles'
10. Carmona, D.; Lamata, M. P.; Sánchez, A. Viguri, F.; Rodríguez, R.; Oro, L. A.; Liu, C.; Díez-González, S.; Maseras, F.
'Chiral transition-metal complexes as Brønsted-acid catalysts for the asymmetric Friedel-Crafts hydroalkoxylation of indoles'
This article is part of the themed collection 'Synergy between experimental and theory'
9. Collinson, J.-M.; Wilton-Ely, J. D. E. T.; Díez-González, S.
'Reusable and highly active supported copper(I)–NHC catalysts for Click chemistry'
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. Markalain-Barta, J.; Díez-González, S.
‘Well-defined diimine copper(I) complexes as catalysts in Click azide-alkyne cycloaddition reactions'
[Invited contribution to special issue on 'Advances in Click Chemistry']
7. ‘On the unique reactivity of Pd(OAc)2 with organic azides: Expedient synthesis of nitriles and imines’
Martínez-Sarti, L.; Díez-González, S.
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.
5. 'Novel phosphinite and phosphonite copper(I) complexes: Efficient catalysts for Click azide-alkyne cycloaddition reactions'
Lal, S.; McNally, J.; White, A. J. P.; Díez-González, S.
In this article, the preparation of novel phosphinite- and phosphonite-bearing copper(I) complexes of the general formula [CuX(L)] is reported.
When compared to well-establised phosphine and phosphite analogues, these compounds displayed improved catalytic activity in the 1,3-dipolar cycloaddition of azides and alkynes. Full optimization of the reaction conditions resulted in a noteworthy Click catalytic system, active under very mild reaction conditions in the absence of any additive and using low metal loadings.
4. Díez-González, S.
‘Well-defined copper(I) complexes for Click azide-alkyne cycloaddition reactions: One Click beyond’
[Hot Article; Invited contribution]
This Perspective was featured in the inside front cover.
3. 'The use of ligands in copper-catalyzed [3+2] azide-alkyne cycloaddition: Clicker than Click chemistry?'
2. ‘[CuBr(PPh3)3] for azide alkyne cycloaddition reactions under true Click conditions’
Lal, S.; Díez-González, S.
In this article we show that commercially available [CuBr(PPh3)3] is an excellent and versatile catalyst for the azide-alkyne cycloaddition reaction and it can indeed be a benchmark catalyst for a broad range of applications.
1. ‘N-Heterocyclic carbenes in copper-catalyzed reactions'
Book chapter in a volume written by 'some of the most talented young chemists in Europe'. This book provides an account of the latest research results in European chemistry based on a selection of leading young scientists participating in the 2008 European Young Chemists Award competition.
29. Díez-González, S.; Escudero-Adán, E. C.; Benet-Buchholz, J.; Stevens, E. D.; Slawin, A. M. Z.; Nolan, S. P. ‘[(NHC)CuX] complexes: Synthesis, characterization and catalytic studies’ Dalton Trans. 2010, 39, 7595–7606.
28. Ramón, R. S.; Bosson, J.; Díez-González, S.; Marion, N.; Nolan, S. P. ‘Au/Ag-cocatalyzed Beckmann rearrangement of aldoximes into primary amides’ J. Org. Chem. 2010, 75, 1197–120 2.
27. Dí ;ez-González, S.; Marion, N.; Nolan , S . P. ‘N-Heterocyclic carbenes in late-transition metals catalysis’ Chem. Rev. 2009, 1 09, 3612–3676.
26. Broggi, J.; Joubert, N.; Díez-González, S.; Berteina-Raboin, S.; Zevaco, T.; Nolan, S. P.; Agrofoglio, L. A. ‘Synthesis of (±)-1,2,3-Triazolo-4’,4-dihydroxymethyl-carbanuclesides’ Tetrahedron 2009, 65, 1162–1170.
25. Teysso t, M.-L.; Jarrousse, A.-S.; Chevry, A.; De Haze, A.; Beaudoin, C.; Manin , M.; Nolan, S. P.; Díez-González, S.; Morel, L.; Gautier, A. ‘Toxicity of copper(I)–NHC against human tumor cells: Induction of cell cycle arrest, apoptosis and DNA cleavage’ Chem.-Eur. J. 2009, 15, 314–318.
24. Díez-González, S.; Nolan, S. P. ‘[(NHC)2Cu]X complexes as efficient cata lysts for azide-alkyne Click chemistry at low catalyst loadings; Angew. Chem., Int. Ed. 2008, 47, 8881–8884.
23. Díez-González, S.; Stevens, E. D.; Nolan, S. P. ‘A [(NHC)CuCl] complex as latent Click catalyst’ Chem. Commun. 2008, 4747–4749.
22. Díez-González, S.; Nolan, S. P. ‘N-Heterocyclic carbene copper complexes: Synthesis and catalysis’ Aldrichimica Acta 2008, 41, 43–51.
21. Díez-González, S.; Paugam, R.; Blanco, L. ‘Synthesis of 1-silabicyclo[4.4.0]dec-5-en-4-ones: A model of A and B rings of 10-silatestosterone’ Eur. J. Org. Chem. 2008, 3298–3307.
20. Díez-González, S.; Blanco, L. ‘Synthesis of 2-methylidene-1-silacyclohexanes by intramolecular hydrosilylation’ J. Organomet. Chem. 2008, 693, 2033–2040.
19. Díez-González, S.; Nolan, S. P. ‘Copper, silver and gold complexes in hydrosilylation reactions’ Acc. Chem. Res. 2008, 41, 349–358.
18. Broggi, J.; Díez-González, S.; Petersen, J. L.; Berteina-Raboin, S.; Nolan, S. P.; Agrofoglio L. A. ‘Study of copper(I) catalysts for the synthesis of carbanucleosides via azide-alkyne 1,3-dipolar cycloaddition’ Synthesis 2008, 141–148 [Feature article].
17. Díez-González, S.; Stevens, E. D., Scott, N. M.; Petersen, J. L.; Nolan, S. P. ‘Synthesis and characterization of [Cu(NHC)2]X complexes: Catalytic and mechanistic studies of hydrosilylation reactions’ Chem.−Eur. J. 2008, 14, 158–168.
16. Díez-González, S.; Nolan, S. P. ‘Transition metal-catalyzed hydrosilylation of carbonyl compounds and imines. A review’ Org. Prep. Proc. Int. 2007, 39, 523–560.
15. Broggi, J.; Joubert, N.; Aucagne, V.; Berteina-Raboin, S.; Díez-González, S .; Nolan, S.: Topalis, D.; Deville-Bonne, D.; Balzarini, J.; Neyts, J.; Andrei, G.; Snoeck, R.; Agrofoglio, L. A. ‘Alkyne-azide click chemistry mediated carbanucleosides synthesis’ Nucleosides, nucleotides and nucleic acids 2007, 26, 1391–1394.
14. Díez-González, S.; Nolan, S. P. ‘[(NHC)Copper(I)] complexes in homogeneous catalysis] Synlett 2007, 2158–2167.
13. Marion, N.; Díez-González S.; Nolan, S. P. ‘N-Heterocyclic carbenes as organocatalysts’ Angew. Chem., Int. Ed. 2007, 46, 2988–3000.
12. Lebel, H.; Davi, M.; Díez-González, S.; Nolan, S. P. ‘Copper-carbene complexes as catalysts in the synthesis of functionalized styrenes and aliphatic alkenes’ J. Org. Chem. 2007, 72, 144–149.
11. Díez-González S.; Nolan, S. P. ‘Stereoelectronic parameters associated with N-heterocyclic carbene (NHC) ligands: A quest for understanding’ Cood. Chem. Rev. 2007, 251, 874–883.
10. Díez-González, S.; Nolan, S. P. ‘Palladium-catalyzed reactions using NHC ligands’ N-Heterocyclic Carbenes in Transition Metal Catalysis: Top. Organomet. Chem. 2007, 21, 47–82.
9. Welle, A.; Díez-González, S.; Tinant, B.; Nolan, S. P.; Riant, O. ‘A three-co mponent tandem reductive a ldol reaction catalyzed by N-heterocyclic carbene-copper complexes’ Org. Lett. 2006, 8, 6059–6062.
8. Díez-González, S.; Correa, A.; Cavallo, L.; Nolan, S. P. ‘(NHC)Copper(I)-catalyzed [3+2] cycloaddition of azides and mono- o r disubstituted alkynes’ Chem.−Eur. J. 2006, 12, 7558–7564.
[Higlighted in Synfacts 2007 (2) 142]
7. Díez-González, S.; Blanco, L. ‘Synthesis of 2-methylidene-1-silacyclohexanes from 2,6-dibromohex-1-ene and polyhalosilanes’ J. Organomet. Chem. 2006, 691, 5531–5539.
6. Marion, N.; Díez-González, S.; de Frémont, P.; Noble, A. R.; Nolan, S. P. ‘AuI-Catal yzed tandem [3,3] rearrangement-intramolecular hydroar ylation: Mild and efficient formation of substitute d indenes’ Angew. Chem., Int. Ed. 2006, 45, 3647–3650 [Hot paper].
5. Díez-González, S.; Scott, N. M.; Nolan, S. P. ‘Cationic copper(I) complexes as e fficient pre-catalysts for the hydrosilylation of carbonyl compounds’ Organometallics 2006, 25, 2355–2358.
4. Díez-González, S.; Nolan, S. P. ‘Palladium pre-catalysts for cross-coupling reactions’ Spec. Chem. Mag. 2006, Jan/Feb, 26–28.
3. Díez-González, S.; Nolan, S. P. ‘Carbene and transition metal-mediated transformations’ Ann. Rep. Prog. Chem., Sect. B 2005, 101, 171–191.
2. Kelly, R. A., III; Scott, N. M.; Díez-González, S.; Stevens, E. D.; Nolan, S. P. ‘Simple synthesis of CpNi(NHC)Cl complexes (Cp = cyclopentadienyl ; NHC = N-heterocyclic carbene)’ Organometallics 2005, 24, 3442–3447.
1. Díez-González, S.; Kaur, H.; Zinn, F. K.; Stevens, E. D.; Nolan, S. P. ‘A simple and efficient copper-catalyzed procedure for the hydrosilylation of hindered and functionalized ketones’ J. Org. Chem. 2005, 70, 4784–4796.