Although homogeneous gold catalysis was known previously, an exponential growth was only induced 12 years ago. The key findings which induce that rise of the field are discussed. This includes early reactions of allenes and furanynes and intermediates of these conversions as well as hydroarylation reactions. Other substrate types addressed are alkynyl epoxides and N-propargyl carboxamides. Important vinylgold intermediates, the transmetalation from gold to other transition metals, the development of new ligands for gold catalysis, and significant contributions from computational chemistry are other crucial points for the field highlighted here.

Gold-Catalyzed Organic Reactions

The ability of platinum and gold catalysts to effect powerful atom-economic transformations has led to a marked increase in their utilization. The quite remarkable correlation of their catalytic behavior with the available structural data, coordination chemistry, and organometallic reactivity patterns, including relativistic effects, allows the underlying principles of catalytic carbophilic activation by π acids to be formulated. The spectrum of reactivity extends beyond their utility as catalytic and benign alternatives to conventional stoichiometric π acids. The resulting reactivity profile allows this entire field of catalysis to be rationalized, and brings together the apparently disparate electrophilic metal carbene and nonclassical carbocation explanations. The advances in coupling, cycloisomerization, and structural reorganization—from the design of new transformations to the improvement to known reactions—are highlighted in this Review. The application of platinum- and gold-catalyzed transformations in natural product synthesis is also discussed.

Catalytic Carbophilic Activation: Catalysis by Platinum and Gold π Acids

1.1. Context and Meta-Review
Despite the ubiquity of metallic gold (Au) in popular culture, its deployment in homogeneous catalysis has only recently undergone widespread investigation. In the past decade, and especially since 2004, great progress has been made in developing efficient and selective Au-catalyzed transformations, as evidenced by the prodigious number of reviews available on various aspects of this growing field. Hashmi has written a series of comprehensive reviews outlining the progression of Au-catalyzed reaction development,1 and a number of more focused reviews provide further insight into particular aspects of Au catalysis. A brief meta-review of the available range of perspectives published on Au catalysis helps to put this Chemical Reviews article in context.

The vast majority of reactions developed with homogeneous Au catalysts have exploited the propensity of Au to activate carbon-carbon π-bonds as electrophiles. Gold has come to be regarded as an exceedingly mild, relatively carbophilic Lewis acid, and the broad array of newly developed reactions proceeding by activation of unsaturated carbon-carbon bonds has been expertly reviewed.2

Further reviews and highlights on Au catalysis focus on particular classes of synthetic reactions. An excellent comprehensive review of Au-catalyzed enyne cycloisomerizations is available.3 Even more focused highlights on hydroarylation of alkynes,4 hydroamination of C-C multiple bonds,5 and reactions of oxo-alkynes6 and propargylic esters7 provide valuable perspectives on progress and future directions in the development of homogeneous Au catalysis.

Most of the reviews on Au catalysis emphasize broad or specific advances in synthetic utility. Recently, we have invoked relativistic effects to provide a framework for understanding the observed reactivity of Au catalysts, in order to complement empirical advancements.8 In this Chemical Reviews article, we attempt to enumerate the ways in which selectivity can be controlled in homogeneous Au catalysis. It is our hope that lessons to guide catalyst selection and the design of new catalysts may be distilled from a thorough evaluation of ligand, counterion, and oxidation state effects as they influence chemo-, regio-, and stereoselectivity in homogeneous Au catalysis.

http://www.cchem.berkeley.edu/toste/publications/cr068430g.pdf

Ligand effects in homogeneous Au catalysis.

This critical review is intended to attract the interest of organic chemists and researchers on green and sustainable chemistry on the catalytic activity of supported gold nanoparticles in organic transformations. In the general part of this critical review, emphasis is given to the different procedures to form supported gold nanoparticles and to the importance of the support cooperating in the catalysis. Also the convergence of homogeneous and heterogeneous catalysis in the study of gold nanoparticles has been discussed. The core part of this review is constituted by sections in which the reactions catalyzed by supported gold nanoparticles are described. Special emphasis is made on the unique ability of gold catalysts to promote additions to multiple C–C bonds, benzannulations and alcohol oxidation by oxygen (282 references).

Supported gold nanoparticles as catalysts for organic reactions

Transition-metal catalysts containing gold present new opportunities for chemical synthesis, and it is therefore not surprising that these complexes are beginning to capture the attention of the chemical community. Cationic phosphine-gold(i) complexes are especially versatile and selective catalysts for a growing number of synthetic transformations. The reactivity of these species can be understood in the context of theoretical studies on gold; relativistic effects are especially helpful in rationalizing the reaction manifolds available to gold catalysts. This Review draws on experimental and computational data to present our current understanding of homogeneous gold catalysis, focusing on previously unexplored reactivity and its application to the development of new methodology.

Relativistic effects in homogeneous gold catalysis

The reaction of carbon-tethered acetylenic aldehydes with alcohols in the presence of a catalytic amount of Pd(OAc)2 in 1,4-dioxane at room temperature gave the 5- or 6-membered acetal products in high yields. The 13C NMR studies suggested that a Pd(II) catalyst exhibited dual roles in the present reaction; the attack of ROH to aldehyde is catalyzed by Lewis acidic Pd(OAc)2, and the nucleophilic oxygen of the resulting hemiacetal reacts with alkyne complexed by Pd(II), giving the alkenyl ethers.

Pd(II) acts simultaneously as a Lewis acid and as a transition-metal catalyst: synthesis of cyclic alkenyl ethers from acetylenic aldehydes.

Pd(II) Acts Simultaneously as a Lewis Acid and as a Transition-Metal Catalyst: Synthesis of Cyclic Alkenyl Ethers from Acetylenic Aldehydes.

Cyclic cross-conjugated hydrocarbons having inserted p-quinoid ring—I

Phenolic oxidative coupling of ethyl 1,2,3,4-tetrahydro-6-hydroxy-1-(3-hydroxy-4-methoxybenzyl)-7-methoxyisoquinoline-2-carboxylate (2c) with potassium ferricyanide afforded the indenoisoquinoline (3c), which rearranged on treatment with acid. Spectral data, and methylation of the rearrangement product and comparison with the dienone (22) obtained from the diazotisation of the aminobenzylisoquinoline (15), followed by photolysis, excluded the morphinan structure (12), and confirmed the dibenz[d,f]indole structure (13).

Syntheses of a proerythrinadienone by phenolic oxidation and a morphinandienone system by a photo-pschorr reaction

Conformation of cyclohexenones

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