Catalysts gold complexes

The gold complex, generated in situ from bis(4-isocyanocyclohexyl)gold(I) tetrafluoroborate and (A)-A-methyl-,V-[2-(dialkylamino)ethyl]-l-[(5)-r,2-bis(diphenylphosphino)ferrocenyl]eth-ylamine, is an effective catalyst for the aldol reaction of various aldehydes with methyl iso-cyanoacetate to give the trans- and cw-4,5-dihydro-l,3-oxazoles. Depending on the aldehyde, the transjeis product ratio ranges from 84 16 to 100 0, and the ee of the main diastereomer is between 72 and 97%26. 

Guzman, J. and Gates, B.C. (2003) Structure and reactivity of a mononuclear gold-complex catalyst supported on magnesium oxide. Angewandte Chemie International Edition, 42, 690-693. 

A mononuclear gold complex catalyst supported on MgO spectroscopic characterization during ethylene... 

Hydroarylations of alkynes are catalyzed by gold complexes and these bear some resemblance to the Fujiwara Pd-catalyzed reaction. In general, when using gold chemistry, better Z/E selectivities are observed compared with palladium, lower catalyst loadings and milder conditions (neutral not TFA) are used. The mechanism involves the attack of ArH on the Au-coordinated alkyne. Flowever, electron-poor acetylenes only appear to work with palladium chemistry (Equations (75) and (76)).72... 

Corma et al. have recently demonstrated the hydrogenation of 145 using a bi-nuclear gold complex of (R,R)-Me-DuPhos [166]. Reasonable rates were observed (TOF 1005 h-1), with the enantioselectivity being higher (75% ee) than that obtained with Pt- and Ir-based catalysts (15% ee in each case). 

Figure 8.1 Gold complex used as catalyst for the hydroamination of axially chiral allenes.

In a joint study by Schmidbaur and Raubenheimer, several phosphine carboxylates and sulfonates of gold and silver were tested as catalysts for the hydration of nonactive alkynes [99]. While the gold complexes showed high activity for these reactions, analogous silver (I) complexes were not active in them. This different behavior was due to the fact that gold cations are weaker acceptors for their ligands and counterions than silver (I) cations (Figure 8.3). 

Only one paper has reported on catalytic asymmetric hydrogenation. In this study by Corma et al., the neutral dimeric duphos-gold(I)complex 332 was used to catalyze the asymmetric hydrogenation of alkenes and imines. The use of the gold complex increased the enantioselectivity achieved with other platinum or iridium catalysts and activity was very high in the reaction tested [195] (Figure 8.5). 

In 1986 Ito, Sawamura, and Hayashi [4] reported that gold(I) complexes prepared from cationic gold complex 1 and chiral ferrocenylphosphine ligands (2) bearing a tertiary amino group at the terminal position of a pendant chain are effective catalysts for asymmetric aldol reaction of... 

Activation of the triple bond of enynes with electrophilic metal derivatives, especially cationic gold complexes, platinum salts such as PtCl2, and ruthenium derivatives, has been reviewed.117 These catalysts make possible nucleophilic addition of the double... 

Some of the catalysts tested are listed in Table 12.13. With only a silver catalyst, the substrate decomposed (entry 1), while AuC13 at least afforded 30% of the product (entry 2). As expected, the coordinatively saturated gold complex gave... 

With gold(III), no conversion was observed (Table 12.16, entry 1) the coordina-tively saturated gold complex gave a low yield of the 6-endo-dig cyclization product (entry 2). The cationic gold complex with a free coordination site gives an excellent yield with the same selectivity (entry 3) the same is true for AgSbF6 alone (entry 4). But this is not true for all silver catalysts with a systematic increase in the pK.A value of the conjugate acid of the silver counterion, increased portions of the 5-exo-dig product were produced (entries 5 and 6). 

Table 4.5 Characteristics of Au/oxide catalysts prepared by deposition of phosphine gold complexes.

The most dramatic results obtained so far with gold catalysts have been with the liquid phase processes. They are conducted with oxygen or air, often using water as solvent, and are therefore felt to be environmentally benign. Particular success has been obtained with reducing sugars (Section 8.3.2) and other aldehydes (Section 8.3.3), and with alcohols and other hydroxy-compounds (Sections 8.3.4-8.3.7). Reactions that use soluble gold complexes to catalyse selective oxidation are reported in Chapter 12. 

Worth mentioning are chiral gold complexes [20d, e] as well as chiral quaternary ammonium fluorides [21], which are used successfully as catalysts in the asymmetric aldol reaction. 

Alkenes act as nucleophiles with alkynes in the presence of gold catalysts. In the most simple version of the reaction, enynes are converted with gold complexes or salts, and in the absence of nucleophiles, into rearranged dienes, cyclopropanated carbocycles, and/or bicyclic cyclobutenes. Depending on the length of the tether and the nature of the substituents, the olefin attack to the alkyne occurs in an endo or an exo fashion (equation 33). Besides, substitution at the alkene plays an important role on the regioselectivity of the nucleophilic attack. ... 

An interesting transformation involving the indole nucleus was found from propargylic carboxylates to give tetracychc compounds with Au(I) (equation 85). This reaction proceeds by an allene-gold complex in equilibrium with the aUcenyl-gold species, which reacts intramolecularly with the indole to form the product. When the reaction of these substrates is performed with dichloro(pyridine-2-carboxylato)gold(III) or Pt(II) as catalysts, products in equation (86) are obtained instead. This new reactivity can be explained by a formal [3 + 2] cycloaddition of 1,3-dipole... 

Guzman, J. and B. C. Gates, Structure and Reactivity of a Mononuclear Gold-Complex Catalyst Supported on Magnesium Oxide , Angew. Chem. Int. Ed., vol 42, Issue 6, pp 690-3. 

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