Alkyne-gold palladium

Hydration and Hydroalkoxylation of Alkynes Gold compounds were first applied to catalyze these types of reactions by Utimoto et al. in 1991, when they studied the use of Au(III) catalysts for the effective activation of alkynes. Previously, these reactions were only catalyzed by palladium or platinum(II) salts or mercury(II) salts under strongly acidic conditions. Utimoto et al. reported the use of Na[AuCI41 in aqueous methanol for the hydration of alkynes to ketones [13]. 

Recently, the Blum group showed that the synthesis of a variety of tri- and tetra-substituted olefins by gold/palladium-catalyzed addition of sp - and sp-hybridized stannanes across monoester and diester alkynes can be accomplished with complete regioselectivity and high stereoselectivity. TTie reaction is proposed to proceed via a bimetallic mechanism where a Lewis acidic gold(I) activates an alkyne toward oxidative addition across palladium(O). 

The NHCs have been used as ligands of different metal catalysts (i.e. copper, nickel, gold, cobalt, palladium, rhodium) in a wide range of cycloaddition reactions such as [4-1-2] (see Section 5.6), [3h-2], [2h-2h-2] and others. These NHC-metal catalysts have allowed reactions to occur at lower temperature and pressure. Furthermore, some NHC-TM catalysts even promote previously unknown reactions. One of the most popular reactions to generate 1,2,3-triazoles is the 1,3-dipolar Huisgen cycloaddition (reaction between azides and alkynes) [8]. Lately, this [3h-2] cycloaddition reaction has been aided by different [Cu(NHC)JX complexes [9]. The reactions between electron-rich, electron-poor and/or hindered alkynes 16 and azides 17 in the presence of low NHC-copper 18-20 loadings (in some cases even ppm amounts were used) afforded the 1,2,3-triazoles 21 regioselectively (Scheme 5.5 Table 5.2). 

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... 

Hydroamination of Alkynes The discovery of palladium-catalyzed intramolecular addition of amines to acetylene coupled with the spectacular contribution of Hutchings opened the door for the synthesis of several nitrogen heterocycles. The first study in this field was performed by Utimoto et al., who researched gold catalyzed intramolecular 6-exo-dig hydroamination. Tautomerization of the initial enamines allowed them to obtain imines, which were thermodynamically more stable [111] (Scheme 8.20). 

The hydration of alkynes is also accomplished by use of catalytic amounts of palladium and gold salts.305 The mildness of this reaction is demonstrated by the preparation of 5-oxo-prostaglandin derivatives (equation 202). In this connection, it should be noted that attempted use of other metal salts to catalyze C—-C triple bond hydrations has met with little success.306... 

The reaction has been done with a palladium catalyst, a titanium catalyst, a tantalum catalyst,and with a gold catalyst. An intramolecular addition of amines to an alkyne unit in the presence of a palladium catalyst generated heterocyclic or cyclic amine compounds.The titanium catalyzed addition of primary... 

The low acidity of 1-alkynes means that strong bases must be used to form the alkynide ions and that water is not a suitable solvent aqueous solutions have a very low concentration of alkynide ions. Some transition metal alkynides can be prepared by precipitation from aqueous solution because their solubilities are very low. Suitable solvents for the preparation of alkynide ions must be less acidic than the alkyne, and preferably allow the alkyne and the alkynide ion to remain in solution. Liquid ammonia, te-trahydrofuran, ether and hydrocarbons have all been used, particularly the first, the alkynide anion being readily formed by metal amides. Alkynides of many types have been prepared from various metals. Besides Groups I and III, copper(I), silver, gold(I), zinc, mercury and, more recently, aluminum alkynides have been synthesized. The alkynides of Groups I and II have been principally used as nucleophiles in alkylation reactions, but there are now many examples of other metal alkynides in this role. Palladium-catalyzed reactions, as remarked above, have become increasingly important for the reactions of alkynides of metals other than Groups I and II, but these have not usually involved alkylation. 

As outlined in previous volumes, the chemistry of ylides coordinated to noble metals, particularly palladium, platinum and gold continues to attract most attention. Refluxing (dppm)palladium(II) dichloride [dppm = bis(diphenylphosphino)methane] with alkynes in mixtures of 1,2-dichloro-ethane/l,4-dioxane provides a novel route to palladium-bound alkenyl phosphorus ylide complexes (53) (Scheme 1)P The reaction represents the... 

The intramolecular hydroarylation of alkynes is a useful method for the synthesis of fused arenes. For example, biphenyl derivatives, bearing an alkyne unit at the ortho position, were converted into substituted phenanthrene derivatives in the presence of various jc-electrophihc transition metal catalysts such as platinum, palladium, gold, gaUium, indium, iron, and so on (Scheme 21.48) [54]. 

The gold-catalyzed alkynylation of heterocycles allowed the functionalizaticm of the most electron-rich position. Nevertheless, this is a limitation if the synthesis of other alkyne regioisomers is desired. In 2013, Waser and co-workers reported that the C2-selective alkynylation of indoles was possible using a palladium catalyst (Scheme 21) [127]. A current limitation of this approach is the requirement for an alkyl substituent on the nitrogen atom. 

The disc-shaped plastic micoreactors, termed microcapillary films (MCFs), contain 19 parallel microchannels, each with a mean internal diameter of 142 10 pm. The material was prepared using a melt extrusion process from an ethylene-vinyl alcohol copolymer (EVOH) [28]. Immobilization of palladium(0) on the wall surface inside the MCFs was performed by simple chemical deposition techniques (Scheme 7.3). The palladium-coated capillaries were used for transfer hydrt enation of ketones, imines, nitro compounds, alkenes, and alkynes with triethylsilane under flow conditions [29]. Microcapillaries whose inside surfaces were coated with copper or gold were also utilized for the continuous-flow reactions [30]. 

---