Review Articles

Gold coordination during homogeneous alkyne and allene cyclisation catalysis: Coordination to substrates, to ancillary ligands and in intermediates

Helgard G. Raubenheimer, Hubert Schmidbaur
South African Journal of Science | Vol 107, No 3/4 | a459 | DOI: https://doi.org/10.4102/sajs.v107i3/4.459 | © 2011 Helgard G. Raubenheimer, Hubert Schmidbaur | This work is licensed under CC Attribution 4.0
Submitted: 05 October 2010 | Published: 16 March 2011

About the author(s)

Helgard G. Raubenheimer, Stellenbosch University, South Africa
Hubert Schmidbaur, Technische Universität München, Germany

Abstract

The ever-increasing role of homogeneous gold catalysis in organic synthesis and the consequent need to be able to rationally control the rate and outcome of such reactions has emphasised the importance of each successive metal–carbon coordination step. Concentrating on alkyne and allene cyclisation and upon reaction mechanisms postulated on the basis of empirical and theoretical results, we have examined the coordination of gold fragments to triple bonds, the modification of gold(I) precatalysts to effect specific reaction pathways or enantioselectivity and the isolation of coordinated intermediates or model compounds thereof. Some of the recent advances that have been made in various laboratories are described in this compact review.

Keywords

gold catalysts; gold complex intermediates; homogeneous catalysis; mechanistic studies; organic synthesis

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References


Schmidbaur H, Schier A. Gold η2-coordination to unsaturated and aromatic hydrocarbons: The key step in gold-catalyzed organic transformations. Organometallics. 2010;29:3–27. doi:10.1021/om900900u

Schmidbaur H, Schier A. Organogold chemistry. In: Crabtree RH, Mingos DMP, editors. Comprehensive organometallic chemistry III. Vol. 2. Oxford: Elsevier, 2006; p. 251–308.

Salvi N, Belpassi L, Tarantelli F. On the Dewar-Chatt-Duncanson model for catalytic gold(I) complexes. Chem Eur J. 2010;16:7231–7239. PMid:20468042

Gorin DJ, Toste FD. Relativistic effects in homogeneous gold catalysis. Nature. 2007;446:395–403. doi:10.1038/nature05592, PMid:17377576

Hashmi ASK. Gold catalyzed organic reactions. Chem Rev. 2007;107:3180–3211. doi:10.1021/cr000436x, PMid:17580975

Arcadi A. Alternative synthetic methods through new developments in catalysis by gold. Chem Rev. 2008;108:3266–3325. doi:10.1021/cr068435d, PMid:18651778

Li Z, Brouwer C, He C. Gold catalyzed organic transformations. Chem Rev. 2008;108:3239–3265. doi:10.1021/cr068434l, PMid:18613729

Gorin DJ, Sherry BD, Toste FD. Ligand effects in homogeneous Au catalysis. Chem Rev. 2008;108:3351–3378. doi:10.1021/cr068430g, PMid:18652511, PMid:2754803

Jiménez-Núñez E, Echavarren AM. Gold-catalyzed cycloisomerizations of enynes: A mechanistic perspective. Chem Rev. 2008;108:3326–3350. doi:10.1021/cr0684319, PMid:18636778

Widenhoefer RA. Recent developments in enantioselective gold(I) catalysis. Chem Eur J. 2008;14:5382–5391. doi:10.1002/chem.200800219, PMid:18442031

Belmont P, Parker E. Silver and gold catalysis for cycloisomerization reactions. Eur J Org Chem. 2009;6075–6089. doi:10.1002/ejoc.200900790

Fürstner A. Gold and platinum catalysis – a convenient tool for generating molecular complexity. Chem Soc Rev. 2009;38:3208–3221. doi:10.1039/b816696j, PMid:19847352

Nevado C. Gold catalysis: Recent developments and future trends. CHIMIA. 2010;64:247–251. doi:10.2533/chimia.2010.247

Sengupta S, Shi X. Recent advances in asymmetric gold catalysis. ChemCatChem. 2010;2:609–619. doi:10.1002/cctc.201000070

. Garcia P, Malacria M, Aubert C, Gandon V, Fensterbank L. Gold-catalysed cross-couplings: New opportunities for C–C bond formation. ChemCatChem. 2010;2:493–497. doi:10.1002/cctc.200900319

De Mendoza P, Echavarren AM. Synthesis of arenes and heteroarenes by hydroarylation reactions catalyzed by electrophilic metal complexes. Pure Appl Chem. 2010;82:801–820. doi:10.1351/PAC-CON-09-10-06

Wu J, Kroll P, Raska Dias HV. Gold(I) chloride coordinated 3-hexyne. Inorg Chem. 2009;48:423–425. doi:10.1021/ic8020854, PMid:19072612

Flügge S, Anoop A, Goddard R, Thiel W, Fürstner A. Structure and bonding in neutral and cationic 14-electron gold alkyne π-complexes. Chem Eur J. 2009;15:8558–8565. doi:10.1002/chem.200901062, PMid:19569141

Nechaev MS, Rayon VM, Frenking G. Energy partitioning analysis of the bonding in ethylene and acetylene complexes of group 6, 8 and 11 metals. J Phys Chem A. 2004;108:3134–3142. doi:10.1021/jp031185+

Garcia-Mota M, Cabello N, Maseras F, Echavarren M, Perez-Ramirez J, Lopez N. Selective homogeneous and heterogeneous gold catalysis with alkynes and alkenes: Similar behaviour and different origin. ChemPhysChem. 2008;9:1624–1629. doi:10.1002/cphc.200800246, PMid:18537219

Akana J, Bhattacharyya KX, Müller P, Sadighi J. Reversible C–F bond formation and the Au-catalyzed hydrofluorination of alkynes. J Am Chem Soc. 2007;129:7736–7737. doi:10.1021/ja0723784, PMid:17547409

Gagosz F. Recent developments in gold catalysis. Tetrahedron. 2009;65:1757–1767. doi:10.1016/j.tet.2008.12.040

Mezailles N, Ricard L, Gagosz F. Phosphine gold(I) bis(trifluoromethanesulfonyl)-imidate complexes as highly efficient and air-stable catalysts for the cycloisomerization of enynes. Org Lett. 2005;7:4133–4136. doi:10.1021/ol0515917, PMid:16146370

Hooper TN, Green M, Russell CA. Cationic Au(I) complexes: Synthesis, structure and reactivity. Chem Commun. 2010;46:2313–2315. doi:10.1039/b923900f, PMid:20234943

Hashmi SAK, Loos A, Littmann A, et al. Gold(I) complexes of KITPHOS monophosphines: Efficient cycloisomerization catalysts. Adv Synth Catal. 2009;351:576–582. doi:10.1002/adsc.200800681

Nieto-Oberhuber C, Pérez-Galán P, Herrero-Gómez E, et al. Gold(I)-catalyzed intramolecular [4 + 2] cycloadditions of arylalkynes or 1,3-enynes with alkenes: Scope and mechanism. J Am Chem Soc. 2008;130:269–279. doi:10.1021/ja075794x, PMid:18076170

Trillo B, López F, Montserrat S, et al. Gold-catalyzed [4C + 3C] intramolecular cycloaddition of allene-dienes: Synthetic protocol and mechanistic implications. Chem Eur J. 2009;15:3336–3339. doi:10.1002/chem.200900164, PMid:19229922

Mauléon P, Zeldin RM, González AZ, Toste FD. Ligand-controlled access to [4 + 2] and [4 + 3] cycloadditions in gold-catalyzed reactions of allene-dienes. J Am Chem Soc. 2009;131:6348–6349. doi:10.1021/ja901649s, PMid:19378998, PMid:2711638

Alonso I, Trillo B, López F, et al. Gold catalyzed [4C + 2C] cycloadditions of allenedienes, including an enantioselective version with new phosphoramidite-based catalysts: Mechanistic aspects of the divergence between [4C + 3C] and [4C + 2C] pathways. J Am Chem Soc. 2009;131:13020–13030. doi:10.1021/ja905415r, PMid:19697936

Benitez D, Tkatchouk E, González AZ, Goddard (III) WA, Toste FD. On the impact of steric and electronic properties of ligands on gold(I)-catalyzed cycloaddition reactions. Org Lett. 2009;11:4798–4801. doi:10.1021/ol9018002, PMid:19780543, PMid:2783583

Alcarazo M, Stork S, Anoop A, Thiel W, Fürstner A. Steering the surprisingly modular π-acceptor properties of N-heterocyclic carbenes: Implications for gold catalysis. Angew Chem Int Ed. 2010;49:2542–2546. doi:10.1002/anie.200907194 PMid:20209549

González A, Toste FD. Gold(I)-catalyzed enantioselective [4 + 2]-cycloaddition of allene-dienes. Org Lett. 2010;12:200–203. doi:10.1021/ol902622b, PMid:19961192, PMid::2798906

Gung BW, Craft DT, Bailey LN, Kirschbaum K. Gold-catalyzed transannular [4 + 3] cycloaddition reactions. Chem Eur J. 2010;16:639–644. doi:10.1002/chem.200902185, PMid:19937623

Zeng X, Frey GD, Kinjo R, Donnadieu B, Bertrand G. Synthesis of a simplified version of stable, bulky and rigid cyclic alkyl(amino) carbenes and catalytic activity of ensuing gold(I) complex in the three-component preparation of 1,2-dihydroquinoline derivatives. J Am Chem Soc. 2009;131:8690–8696. doi:10.1021/ja902051m, PMid:19456108, PMid::2724870

Zeng X, Kinjo R, Donnadieu B, Bertrand G. Serendipitous discovery of the catalytic hydroammoniumation and methylamination of alkynes. Angew Chem Int Ed. 2010;49:942–945.

Bartholomé C, Ramiro Z, Pérez-Galán P, et al. Gold(I) complexes with hydrogen-bond supported heterocyclic carbenes as active catalysts in reactions of 1,6-enynes. Inorg Chem. 2008;47:11391–11397. doi:10.1021/ic801446v, PMid:18947178

Minghetti G, Bonati F. Bis(carbene) complexes of gold(I) and gold(III). J Organomet Chem. 1973;54:C62-C63.

Bartolomé C, Ramiro Z, Garcia-Cuadrado D, et al. Nitrogen acyclic gold(I) carbenes: Excellent and easily accessible catalysts in reactions of 1,6-enynes. Organometallics. 2010;29:951–956. doi:10.1021/om901026m

Hashmi SAK, Hengst T, Lothschütz C, Rominger F. New and easily accessible nitrogen acyclic gold(I) carbenes: Structure and application in the gold-catalyzed phenol synthesis as well as the hydration of alkynes. Adv Synth Catal. 2010;352:1315–1337. doi:10.1002/adsc.201000126

Hashmi SAK, Ramamurthi TD, Rominger F. Synthesis, structure and reactivity of organogold compounds of relevance to homogeneous gold catalysis. J Organomet Chem. 2009;694:592–597. doi:10.1016/j.jorganchem.2008.11.054

Partyka DV, Zeller M, Hunter AD, Gray TG. Relativistic functional groups: Aryl carbon-gold bond formation by selective transmetalation of boronic acids. Angew Chem Int Ed. 2006;45:8188–8191. doi:10.1002/anie.200603350, PMid:17111449

Liu L-P, Hammond GB. Reactions of cationic gold(I) with allenoates: Synthesis of stable organogold(I) complexes and mechanistic investigations on gold-catalyzed cyclizations. Chem Asian J. 2009;4:1230–1236. doi:10.1002/asia.200900091, PMid:19472292

Hashmi ASK, Lothschütz C, Döpp R, Rudolph M, Ramamarthi TD, Rominger F. Gold and palladium combined for cross-coupling. Angew Chem Int Ed. 2009;48:8243–8246. doi:10.1002/anie.200902942, PMid:19790218

Weber D, Tarselli MA, Gagné MR. Mechanistic surprises in the gold(I)-catalyzed intramolecular hydroarylation of allenes. Angew Chem Int Ed. 2009;48:5733–5736. doi:10.1002/anie.200902049, PMid:19562821, PMid:2978329

Cheong PH, Morganelli P, Luzung MR, Houk KN, Toste FD. Gold-catalyzed cycloisomerization of 1,5-allenynes via dual activation of an ene reaction. J Am Chem Soc. 2008;130:4517–4526. doi:10.1021/ja711058f, PMid:18327944, PMid:2995695

Hashmi ASK, Schuster A, Rominger F. Gold catalysis: Isolation of vinylgold complexes derived from alkynes. Angew Chem Int Ed. 2009;48:8247–8249. doi:10.1002/anie.200903134, PMid:19768822

Hashmi ASK, Ramamurthi TD, Rominger F. On the trapping of vinylgold intermediates. Adv Synth Catal. 2010;352:971–975. doi:10.1002/adsc.201000011

Strasser CE, Stander-Grobler E, Schuster O, Cronje S, Raubenheimer HG. Preparation of remote NHC complexes of rhodium(I) and gold(I) by ligand transfer. Eur J Inorg Chem. 2009;1905–1912. doi:10.1002/ejic.200801180

Raubenheimer H, Cronje S. Carbene complexes of gold: Preparation, medical application and bonding. Chem Soc Rev. 2008;37:1998–2011. doi:10.1039/b708636a, PMid:18762843

Solorio-Alvarado CR, Echavarren AM. Gold-catalyzed annulation/fragmentation: Formation of free gold carbenes by retro-cyclopropanation. J Am Chem Soc. 2010;132:11881–11883. doi:10.1021/ja104743k, PMid:20698529

Binger P, Müller P, Benn R, et al. Vinylcarbene complexes of titanocene. Angew Chem Int Ed Engl. 1989;28:610–611. doi:10.1002/anie.198906101

Nguyen ST, Johnson LK, Grubbs RH. Ring-opening metathesis polymerization (ROMP) of norbornene by a group VIII carbene complex in protic media. J Am Chem Soc. 1992;114:3974–3975. doi:10.1021/ja00036a053

Seidel G, Mynott R, Fürstner A. Elementary steps of gold catalysis: NMR spectroscopy reveals the highly cationic character of a “gold carbenoid”. Angew Chem Int Ed. 2009;48:2510–2513. doi:10.1002/anie.200806059, PMid:19248070

Schuster O, Yang L, Raubenheimer HG, Albrecht M. Beyond conventional N-heterocyclic carbenes: Abnormal, remote, and other classes of NHC ligands with reduced heteroatom stabilization. Chem Rev. 2009;109:3445–3478. doi:10.1021/cr8005087, PMid:19331408

Raubenheimer HG, Esterhuysen MW, Timoshkin A, Chen Y, Frenking G. Electrophilic addition of Ph3PAu+ to anionic alkoxy Fischer-type carbene complexes: A novel approach to metal stabilised bimetallic vinyl ether complexes. Organometallics. 2002;21:3173–3181. doi:10.1021/om020048g,

Raubenheimer HG, Esterhuysen MW, Frenking G, et al. Aurolysis of a-C-deprotonated group 6 aminocarbene and thiocarbene complexes with Ph3PAu+. Dalton Trans. 2006; 4580–4589. doi:10.1039/b607613k, PMid:17016569

Fürstner A, Morency L. On the nature of the reactive intermediates in gold-catalyzed cycloisomerization reactions. Angew Chem Int Ed. 2008;47:5030–5033. doi:10.1002/anie.200800934, PMid:18504793

Hashmi SAK. “High noon” in gold catalysis: Carbene versus carbocation intermediates. Angew Chem Int Ed. 2008;47:6754–6756. doi:10.1002/anie.200802517, PMid:18683174

Roth KE, Blum S. Relative kinetic basicities of organogold compounds. Organometallics. 2010;29:1712–1716. doi:10.1021/om901101f

Smith MB, March J. March’s advanced organic chemistry: Reactions, mechanisms and structure. 5th ed. New York: John Wiley & Sons, 2001; p. 329.



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