Gold catalyzes the Sonogashira coupling reaction without the requirement of palladium impurities

Corma, Avelino; Juárez, Raquel; Boronat, Mercedes; Sánchez, Félix; Iglesias, Marta; Garcı́a, Hermenegildo

doi:10.1039/c0cc04564k

Cited by 168 publications

(118 citation statements)

References 12 publications

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“…[7] Recently it has been suggested that gold nanoparticles formed during the reaction could act as heterogeneous catalysts in these transformations. [8] An alternative approach to access Au I /Au III catalytic cycles under homogeneous conditions is to use a sacrificial external oxidant to perform the key oxidation of gold(I) to goldA C H T U N G T R E N N U N G (III). [9] A general mechanism for such processes is shown in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Au^I/Au^III Catalysis: An Alternative Approach for CC Oxidative Coupling

Hopkinson

Gee

Gouverneur

2011

Chemistry A European J

316

119

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When reacted in the presence of external oxidants, gold complexes are capable of catalyzing oxidative homo- and cross-coupling reactions involving the formation of new C-C bonds. Over the last few years, several cascade processes have been reported in which coupling is preceded by a gold-mediated aryl C-H functionalization or nucleophilic addition. These reactions combine the unique reactivity of gold with oxidative coupling, enabling the construction of C-C bonds between coupling partners that are not easily accessed using alternative catalysts. In this Concept paper, the development of gold-catalyzed oxidative coupling reactions is discussed focusing on C-C bond-forming reactions of broad synthetic appeal.

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Section: Introductionmentioning

confidence: 99%

Au^I/Au^III Catalysis: An Alternative Approach for CC Oxidative Coupling

Hopkinson

Gee

Gouverneur

2011

Chemistry A European J

316

119

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“…On the basis of DFT calculation, Corma and coworkers have also proposed that a similar type of oxidative addition process occurs during the reaction of iodobenzene with Au 38 . 15 In summary, we have demonstrated anomalous behavior of bimetallic Au/Pd alloy systems in the coupling reaction of PhB(OH) 2 with CBA at room temperature under aqueous conditions. The most important finding is that the reaction mechanism is likely to be completely different from that of the conventional SuzukiMiyaura coupling, which can be described in terms of the participation of a single metal (Pd).…”

mentioning

confidence: 99%

Anomalous Efficacy of Bimetallic Au/Pd Nanoclusters in C–Cl Bond Activation and Formal Metathesis-type C–B Bond Activation at Room Temperature

Dhital

Sakurai

2012

Chemistry Letters

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Au/Pd alloy nanoclusters stabilized by poly(N-vinylpyrrolidone) catalyze two different reactions of phenylboronic acid with 4-chlorobenzoic acid at room temperature in a single reaction cycle, cross coupling and metathesis-type homocoupling that is normally inaccessible through conventional catalysis.Bimetallic nanoclusters with an alloy structure have attracted a great deal of interest during the past decade owing to their enhanced catalytic activities, which are superior to those of the corresponding monometallic counterparts.1,2 Among the various bimetallic nanoclusters fabricated to date, Au/Pd alloy clusters are particularly fascinating because of their excellent catalytic activities for a diversity of chemical transformations. Recent research reports have, however, dealt mainly with the significant extension of catalytic reactivity and selectivity of monometallic nanoclusters.3,4 Herein, we report the peculiar catalytic activity of bimetallic Au/Pd alloyed nanoclusters in coupling between 4-chlorobenzoic acid (CBA) and phenylboronic acid (PhB(OH) 2 ) under aqueous conditions at room temperature.Among the organic halides including triflates, organic chlorides are less reactive due to relatively high CCl bond strength and their reluctance to undergo oxidative addition. Recently significant progress has been made toward activation of aryl chlorides by the use of highly electron-donative and bulky ligands.5 These ligands make the metal more nucleophilic, which facilitates oxidative addition by less active CCl bonds, the initial step of cross-coupling reaction. We previously reported that colloidal gold nanoclusters, such as poly(Nvinylpyrrolidone)-protected gold (Au:PVP) or chitosan [¢-1,4-linked poly(D-glucosamine)]-protected gold (Au:chit), are excellent catalysts for aerobic oxidation including homocoupling reactions of arylboronic acids and their derivatives (cycle B in Scheme 1) in water under ambient conditions. 6,7 One characteristic feature of colloidal nanogold is that a negatively charged surface is generated due to the size effect of the clusters as well as the donation effect from the matrices, realizing the facile adsorption of molecular oxygen on its surface.8 Such electronically enriched cluster surface would also be expected to accelerate the oxidative addition process in the SuzukiMiyaura cross coupling (cycle A in Scheme 1). Since Pd always favors the cross coupling against homocoupling as compared with Au, we started to develop PVP-stabilized bimetallic Au/Pd alloy clusters for the activation of CCl bond under mild conditions in the SuzukiMiyaura reaction. The PVP-stabilized Au and Pd monometallic and bimetallic alloy clusters containing 1:1 ratios of two metals (Au 0.5 Pd 0.5 :PVP) were prepared according to our previous procedure. First, the coupling reactions between CBA and PhB(OH) 2 by monometallic clusters were investigated. Equimolar amounts of CBA and PhB(OH) 2 were used as reactants. The crosscoupling product, biphenyl-4-carboxylic acid (1) was not observed, but biphenyl (2) and phe...

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“…[24] Importantly, control reactions [25] indicated the need for both the acid and the oxidant, as well as a gold precatalyst; the failure of palladium, and various other late transition metals, to catalyse the transformation provided evidence against low-level impurities being responsible for the catalytic activity ascribed to gold. [26] Subsequent reaction optimisation [25] revealed that both Au I and Au III species-as well-defined complexes, simple salts or in combination with Ag I salts-were able to act as precatalysts for the IBA/p-TSA-mediated oxyarylation ( Table 2, entries 1-12). As with our previously reported methodology, [9] the reaction was sensitive to the steric and electronic environment about the gold centre: [AuClA C H T U N G T R E N N U N G (PPh 3 )] proved a more efficient precatalyst than complexes of bulky and/or strong donor ligands (entry 1 vs. entries 6-10).…”

Section: Resultsmentioning

confidence: 99%

Gold‐Catalysed Oxyarylation of Styrenes and Mono‐ and gem‐Disubstituted Olefins Facilitated by an Iodine(III) Oxidant

Ball

Lloyd‐Jones

Russell

2012

Chemistry A European J

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1-Hydroxy-1,2-benziodoxol-3(1H)-one (IBA) is an efficient terminal oxidant for gold-catalysed, three-component oxyarylation reactions. The use of this iodine(III) reagent expands the scope of oxyarylation to include styrenes and gem-disubstituted olefins, substrates that are incompatible with the previously reported Selectfluor-based methodology. Diverse arylsilane coupling partners can be employed, and in benzotrifluoride, homocoupling is substantially reduced. In addition, the IBA-derived co-products can be recovered and recycled.

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Gold catalyzes the Sonogashira coupling reaction without the requirement of palladium impurities

Abstract: By a combination of kinetic and theoretical studies it is concluded that gold is intrinsically active to perform the Sonogashira coupling reaction between phenylacetylene and iodobenzene. The presence of Pd impurities is not mandatory for catalyst activity.

Cited by 168 publications

References 12 publications

Au^I/Au^III Catalysis: An Alternative Approach for CC Oxidative Coupling

Au^I/Au^III Catalysis: An Alternative Approach for CC Oxidative Coupling

Anomalous Efficacy of Bimetallic Au/Pd Nanoclusters in C–Cl Bond Activation and Formal Metathesis-type C–B Bond Activation at Room Temperature

Gold‐Catalysed Oxyarylation of Styrenes and Mono‐ and gem‐Disubstituted Olefins Facilitated by an Iodine(III) Oxidant

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Gold catalyzes the Sonogashira coupling reaction without the requirement of palladium impurities

Abstract: By a combination of kinetic and theoretical studies it is concluded that gold is intrinsically active to perform the Sonogashira coupling reaction between phenylacetylene and iodobenzene. The presence of Pd impurities is not mandatory for catalyst activity.

Cited by 168 publications

References 12 publications

AuI/AuIII Catalysis: An Alternative Approach for CC Oxidative Coupling

AuI/AuIII Catalysis: An Alternative Approach for CC Oxidative Coupling

Anomalous Efficacy of Bimetallic Au/Pd Nanoclusters in C–Cl Bond Activation and Formal Metathesis-type C–B Bond Activation at Room Temperature

Gold‐Catalysed Oxyarylation of Styrenes and Mono‐ and gem‐Disubstituted Olefins Facilitated by an Iodine(III) Oxidant

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Au^I/Au^III Catalysis: An Alternative Approach for CC Oxidative Coupling

Au^I/Au^III Catalysis: An Alternative Approach for CC Oxidative Coupling