Palladium-Catalyzed Synthesis of 1,3-Dienes from Allenes and Organic Halides

A wide range of aryl and vinylic halides react with 1,1-dimethylallene (2a) and potassium carbonate in the presence of Pd(dba)(2) (dba = dibenzylideneacetone) in N,N-dimethylacetamide (DMA) at temperature 100-120 degrees C to give the corresponding dienes CH(2)C(CH(3))CRCH(2) (3a-o), where R is aryl or vinylic, in good to excellent yields. Higher yields of diene products were obtained for aryl bromides than for the corresponding aryl iodides and chlorides. Under similar reaction conditions, tetramethylallene (2b), 1-methyl-1-phenylallene (2c), 1-methyl-3-phenylallene (2d), and 1-cyclohexylallene (2e) also react with aryl and vinylic halides to give diene products (3p-w). For 2d, both E and Z isomers 3t and 3u of the diene product were observed. For 2e, two regioisomers 3vand 3w were isolated with 3w likely from alkene isomerization of 3v. Various palladium systems were tested for the catalytic activity of diene formation. In addition to Pd(dba)(2)/PPh(3), Pd(OAc)(2)/PPh(3), PdCl(2)(PPh(3))(2), and PdCl(2)(dppe) are also very effective as catalysts for the reaction of 2a with p-bromoacetophenone (1a) to give 3a. Studies on the effect of solvents and bases show that DMA and K(2)CO(3) are the solvent and base that give the highest yield of diene 3a. Possible mechanisms for this catalytic diene formation are proposed.     

C-C coupling reactions of aryl bromides and arylsiloxanes in water catalyzed by palladium complexes of phosphanes modified with crown ethers

[reaction: see text] The complexes [PdCl2L2], where L is a crown-ether-containing triarylphosphane, catalyze the formation of biaryls from arylsiloxanes and aryl bromides with high yields in water as solvent and under air. The water-insoluble catalysts [PdCl2(PhCN)2] and [PdCl2(PPh3)2] are also efficient, although they decompose more quickly to form black Pd0.     

NiCl(2)(dppe)-catalyzed cross-coupling of aryl mesylates, arenesulfonates, and halides with arylboronic acids

An investigation of the NiCl(2)(dppe)-, NiCl(2)(dppb)-, NiCl(2)(dppf)-, NiCl(2)(PCy(3))(2)-, and NiCl(2)(PPh(3))(2)-catalyzed cross-coupling of the previously unreported aryl mesylates, and of aryl arenesulfonates, chlorides, bromides, and iodides containing electron-withdrawing and electron-donating substituents with aryl boronic acids, in the absence of a reducing agent, is reported. NiCl(2)(dppe) was the only catalyst that exhibited high and solvent-independent activity in the two solvents investigated, toluene and dioxane. NiCl(2)(dppe) with an excess of dppe, NiCl(2)(dppe)/dppe, was reactive in the cross-coupling of electron-poor aryl mesylates, tosylates, chlorides, bromides, and iodides. This catalyst was also efficient in the cross-coupling of aryl bromides and iodides containing electron-donating substituents. Most surprisingly, the replacement of the excess dppe from NiCl(2)(dppe)/dppe with excess PPh(3) generated NiCl(2)(dppe)/PPh(3), which was found to be reactive for the cross-coupling of both electron-rich and electron-poor aryl mesylates and chlorides. Therefore, the solvent-independent reactivity of NiCl(2)(dppe) provides an inexpensive and general nickel catalyst for the cross-coupling of aryl mesylates, tosylates, chlorides, bromides, and iodides with aryl boronic acids.     

Palladium(II) thiocarboxamide complexes: synthesis, characterisation and application to catalytic Suzuki coupling reactions

A simple route to synthesise palladium(II) complexes from the reaction of N-substituted pyridine-2-thiocarboxamide ligands and PdCl(2)(PPh(3))(2) has been developed. The new complexes are very soluble in common solvents and have been fully characterised (elemental analysis, FT-IR, (1)H, (31)P, (13)C-NMR), including an X-ray diffraction analysis. The molecular structures of all the complexes were determined and reveal the presence of square planar geometry around Pd with little distortion. The complexes were tested in the Suzuki coupling of electronically deactivated aryl and heteroaryl bromides and were found to have much greater activity, without using any promoting additives or phase transfer agent under aerobic conditions. Higher reaction rates are obtained by varying R substituents on the aromatic ring of pyridine-2-thiocarboxamide. The effect of other variables on the cross-coupling reaction, such as temperature, solvent and base, is also reported.     

N6-Arylation of 2'-deoxyadenosine via copper-catalyzed direct coupling with aryl halides

[reaction: see text] A general method for efficient N(6)-arylation of 2'-deoxyadenosine via copper-catalyzed direct coupling with aryl iodides and bromides is described. The method is useful for aryl halides with either electron-donating or electron-withdrawing groups.     

Improvements in cross coupling reactions of hypervalent siloxane derivatives

[formula: see text] The scope of the palladium-catalyzed cross coupling reaction of aryl halides with phenyltrimethoxysilane has been expanded to include aryl bromides, heteroaryl bromides, and aryl chlorides. A more general Pd(0)-catalyst/ligand system has been developed to activate bromides: palladium(II) acetate (Pd(OAc)2) is activated with triphenylphosphine (PPh3) or tri-o-tolylphosphine (P(o-tol)3) (1:2 molar ratio of Pd:phosphine). Coupling of aryl chloride derivatives required addition of 2-(dicyclohexylphosphino)biphenyl (Buchwald's ligand) to Pd2dba3 (tris-(dibenzylideneacetone)dipalladium(0)) (1:1.5 molar ratio of Pd:phosphine).     

Facile synthesis of symmetrical functionalized biaryls from aryl halides catalyzed by commercial zinc dust using ammonium formate

Reductive homocoupling of aryl halides in the presence of commercial zinc dust and ammonium formate in methanol produces biaryls in good to excellent yields. Aryl halides having either electron-donating or electron-withdrawing groups underwent smooth coupling to afford the corresponding symmetrical biaryls. Addition of 1 equiv of sodium hydroxide enhanced the coupling reaction rate. Commercial zinc dust is inexpensive, widely available and can be used without any auxiliary catalysts such as Pd(0) and/or Ni(0).     

环钯化二茂铁亚胺-三苯基膦配合物的合成、表征及催化Suzuki反应研究

为筛选高效催化Suzuki反应的催化剂, 合成了3种新的环钯化二茂铁亚胺-三苯基膦配合物2~4, 经元素分析(或HRMS)、 红外光谱和核磁共振谱对其结构进行了表征, 并通过X射线单晶衍射测定了化合物3的晶体结构. 这些化合物容易合成, 在空气和溶液中稳定, 可用作芳基溴及杂芳基溴与苯基硼酸偶联的Suzuki反应催化剂. 使用摩尔分数为0.01%的催化剂3, 以2倍量的K3PO4为碱, 于110 ℃下, 在甲苯中反应5~15 h, 使具有不同电子和位阻效应的取代芳基溴及杂芳基溴能以较高的产率与苯基硼酸反应生成偶联产物; 与溴苯相比, 带吸电子基的溴苯反应活性较高, 催化剂的摩尔分数降低至0.001%时, 仍能得到较高产率, 而带强给电子基的溴苯如4-溴苯甲醚及带邻位取代基的溴苯在其它条件相同时, 需要延长反应时间才能得到较高的产率.     

Efficient Stille cross-coupling reaction using aryl chlorides or bromides in water

An efficient Stille cross-coupling reaction using a variety of aryl halides in neat water has been developed. Employing palladium-phosphinous acid catalyst [(t-Bu)(2)P(OH)](2)PdCl(2) allows formation of biaryls from aryl chlorides and bromides in good to high yields. Functional groups such as ketones and nitriles are tolerated, and organic cosolvents are not required. The air stability and solubility in water of the palladium complexes used in this study facilitate operation of the coupling reaction and product isolation. The feasibility of catalyst recycling has also been demonstrated.     

Mono- and binuclear cyclometallated palladium(II) complexes containing bridging (N,O-) and terminal (N-) imidate ligands: air stable, thermally robust and recyclable catalysts for cross-coupling processes

Novel dinuclear cyclometallated palladium complexes [{Pd(mu-NCO)(C circumflex accent N)}(2)], containing asymmetric imidato -NCO- bridging units have been synthesised [C circumflex accent N = 7,8-benzoquinolyl; -NCO- = succinimidate (1c), phthalimidate (1a-3a) or maleimidate (3c)]. The reaction of these complexes, and the previously reported analogous imidate precursors containing a phenylazophenyl (1a-3a) or 2-pyridylphenyl (1b-3b) backbone, with tertiary phosphines provides novel mononuclear N-bonded imidate derivatives of the general formula [Pd(C circumflex accent N)(imidate)(L)][L = PPh(3), P(4-F-C(6)H(4))(3) or P(4-MeO-C(6)H(4))(3)]. The single crystal structures of [Pd(azb)(phthalimidate)(P(4-MeO-C(6)H(4))(3))](9a) and [Pd(bzq)(phthalimidate)(PPh(3))](7c) have been established. Dinuclear complexes (1a-3a, 1b-3b, 1c-3c) demonstrate outstanding thermal stability in the solid-state, as shown by thermoanalytical techniques. A marked influence of bridging imidate groups on the initial decomposition temperature is observed. The dinuclear and mononuclear derivatives are shown to be active catalysts/precatalysts for the Suzuki-Miyaura cross-coupling reactions of aryl bromides with aryl boronic acids, and the Sonogashira reactions of aryl halides with phenyl acetylene (in the presence and absence of Cu(I) salts). The conversions appear to be dependent, to some extent, on the type of imidate ligand, suggesting a role for these pseudohalides in the catalytic cycle in both cross-coupling processes. Lower catalyst loadings in 'copper-free' Sonogashira cross-couplings favour higher turnover frequencies. We have further determined that these catalysts may be recycled using a poly(ethylene oxide)(PEO)/methanol solvent medium in Suzuki-Miyaura cross-coupling. Once the reaction is complete, product extraction into a hexane/diethyl ether mixture (1 : 1, v/v) gives cross-coupled products in good yields (with purity > 95%). The polar phase can then be re-used several times without appreciable loss of catalytic activity.     

Cross-coupling reactions of (1-fluorovinyl)methydiphenylsilane(1) with aryl halides and aryl triflates

The cesium fluoride (CsF)-assisted cross-coupling reaction of (1-fluorovinyl)methyldiphenylsilane (1) with aryl halides and aryl triflates was examined. The reaction with aryl iodides smoothly proceeded to afford the corresponding (1-fluorovinyl)arenes in the presence of a catalytic amount of CuI and Pd(PPh(3))(4) in aprotic polar solvents such as DMF, DMI, DMA, and NMP in good yields. A variety of functional groups (nitro, ester, ketone, and ether) on the aromatic rings can be tolerated under these mild conditions. Aryl iodides are superior to aryl bromides as the coupling reaction partner. The cross-coupling reaction of 1 with aryl triflates instead of aryl halides was also accomplished in the presence of tetrabutylammonium iodide (n-Bu(4)NI) as the additive under similar conditions.     

Efficient synthesis of 4-(2'-alkenyl)-2,5-dihydrofurans and 5,6-dihydro-2H-pyrans via the Pd-catalyzed cyclizative coupling reaction of 2,3- or 3,4-allenols with allylic halides

In the absence of a base, palladium(II) catalysts, such as PdCl(2), PdCl(2)(CH(3)CN)(2), Pd(OAc)(2), and [(pi-C(3)H(5))PdCl](2), can catalyze the cyclizative coupling reaction of 2,3- or 3,4-allenols with allylic halides in DMA at room temperature to provide 2,5-dihydrofurans and 5,6-dihydro-2H-pyrans, respectively, in moderate to good yields. Under similar reaction conditions, nonsubstituted 2,3-allenol 1s affords bimolecular cyclizative coupling product 5s as the major product. The scope of the reaction and its mechanism have been studied briefly. On the basis of the experimental results, the transformation was believed to proceed via a divalent palladium-catalyzed pathway.     

(t-Bu)2PN=P(i-BuNCH2CH2)3N: new efficient ligand for palladium-catalyzed C-N couplings of aryl and heteroaryl bromides and chlorides and for vinyl bromides at room temperature

By employing Pd(OAc)2, Cs2CO3, or NaOH, and the new ligand (t-Bu)2PN=P(i-BuNCH2CH2)3N (3a), an electronically diverse array of aryl bromides and chlorides possessing base-sensitive substituents (nitro, ester, and keto) provide coupling products with bulky aryl amines in good to excellent yields. Aryl halides possessing other functional groups including cyano, amino, trifluoromethyl, and phenol, coupled with equal ease, producing highly functionalized amines in good to excellent yields. Moreover, an aryl chloro group can be preserved in the presence of a bromo substituent under our reaction conditions. BOC-protected amines also participated efficiently. Heterocyclic bromides and chlorides underwent clean couplings with amines in excellent yields. An important strength of our protocol is the use of lower palladium loadings than those reported earlier, without compromising yields. The air-stable palladium complex (eta3-cinnamyl)PdCl.(3a) (5) was also employed successfully in C-N coupling reactions while the crotyl analogue was less efficacious. The 3a/Pd(OAc)2 catalyst system promotes, for the first time, efficient coupling of vinyl bromides with a variety of amines to produce imines and enamines at room temperature.     

An efficient Approach to Modify the Catalyst Activity for the Hydrogenation of Nitrobenzene

Transition metal complexes have been used extensively for the hydrogenation in homogeneous system probably due to their high catalytic selectivities under mild operating conditions. In order to improve the homogeneous catalyst system, some studies on the homogeneous or soluble polymer-supported bimetallic catalysts have been recently carried out and enhanced activity, better selectivity were observed in selective hydrogenation, hydrodehalogenation, carbonylation, hydroformylation and regioselec…     

Chemistry of palladium phosphinite (PPh(2)(OR)) and phosphonite (P(OPh)(2)(OH)) complexes: catalytic activity in methoxycarbonylation and Heck coupling reactions

The new phosphinite and phosphonite complexes (1-8) are very efficient catalysts for the methoxycarbonylation of iodobenzene and Heck cross-coupling of bromobenzene with butyl acrylate. High catalytic activity of these complexes can be explained by their in situ transformations during the reaction, stimulated by the presence of water, acid (HCl) or base (NEt(3)). Hydrolysis of phosphinite palladium complexes of the form trans-PdCl(2)[PPh(2)(OR)](2) (R = C(6)F(5), 2, (t)Bu 3, or O-menthyl 4) results in the formation of the dimeric complex [mu-ClPd(PPh(2)OH)(PPh(2)O)](2) 5, which is deprotonated by NEt(3), producing a polymeric complex of formula [Pd(P(O)PPh(2))(2)](n) 8. The reverse reaction, protonolysis of 8 with HCl, leads back to 5 and the monomeric complex 5a. The phosphinite complex PdCl(2)[PPh(2)(OBu)](2)1 with a more lipophilic ligand, PPh(2)(OBu), does not undergo hydrolysis under the same conditions. In the reaction of PdCl(2)(cod) with P(OPh)(2)(OH), the new dimer [mu-ClPd(P(OPh)(2)OH)(P(OPh)(2)O)](2) 6 was obtained, whereas reaction of Pd(OAc)(2) with P(OPh)(2)(OH) leads to the polymeric complex [Pd[P(O)(OPh)(2)](2)](n) 7. Protonolysis of 7 with HCl results in the formation of 6.     

Cp2Fe(PR2)2PdCl2 (R = i-Pr, t-Bu) complexes as air-stable catalysts for challenging Suzuki coupling reactions

[reaction: see text] The use of Cp(2)Fe(PR(2))(2)PdCl(2) (R = i-Pr and t-Bu) in Suzuki coupling reactions were illustrated using a high throughput screening approach. The di-tbpfPdCl(2) catalyst was shown to be the more active catalyst for unactivated and sterically challenging aryl chlorides. Comparison studies using the commercial catalysts dppfPdCl(2), (Ph(3)P)(2)PdCl(2), (Cy(3)P)(2)PdCl(2), DPEPhosPdCl(2), dppbPdCl(2), dppePdCl(2), Pd(t-Bu(3)P)(2), and [Pd(mu-Br)(t-Bu(3)P)](2) were also done for selected cases to demonstrate the superior activities of di-tbpfPdCl(2) and di-isoppfPdCl(2).     

Palladium-catalyzed homocoupling of aryl halides in the presence of fluoride

This report describes the fluoride-mediated homocoupling of aryl iodides and bromides catalyzed by palladium(0). This coupling protocol is tolerant of electron-donating and electron-withdrawing substitutents on the aryl halide, as well as ortho substitution. Optimum reaction conditions entail 10 mol% Pd(dba)₂, 3 equiv of tetrabutyl ammonium fluoride (TBAF) in DMF at 90 °C.     

Controlled synthesis of hydroxyapatite-supported palladium complexes as highly efficient heterogeneous catalysts

Achieving precise control of active species on solid surfaces is one of the most important goals in the development of highly functionalized heterogeneous catalysts. The treatment of hydroxyapatites with PdCl(2)(PhCN)(2) gives two new types of hydroxyapatite-bound Pd complexes. Using the stoichiometric hydroxyapatite, Ca(10)(PO(4))(6)(OH)(2), we found that monomeric PdCl(2) species can be grafted on its surface, which are easily transformed into Pd(0) particles with narrow size distribution in the presence of alcohols. Such metallic Pd species can effectively promote alcohol oxidation using molecular oxygen and are shown to give a remarkably high TON of up to 236 000. Another monomeric Pd(II) phosphate complex can be generated at a Ca-deficient site of the nonstoichiometric hydroxyapatite, Ca(9)(HPO(4))(PO(4))(5)(OH), affording a catalyst with Pd(II) structure and high activity for the Heck and Suzuki reactions. To the best of our knowledge, the PdHAP are one of the most active heterogeneous catalysts for both alcohol oxidation under an atmospheric O(2)() pressure and the Heck reaction reported to date. These Pd catalysts are recyclable in the above organic reactions. Our approach to catalyst preparation based on the control of Ca/P ratios of hydroxyapatites represents a particularly attractive method for the nanoscale design of catalysts.     

Palladium-catalyzed cross-coupling of B-benzyl-9-borabicyclo[3.3.1]nonane to furnish methylene-linked biaryls

[reaction: see text] Benzylboranes are noticeably uncommon partners within Suzuki-Miyaura coupling reactions. B-Benzyl-9-BBN was successfully coupled to a range of aryl/heteroaryl bromides, chlorides, and triflates to give pharmacologically important methylene-linked biaryl structures. Activated, deactivated, and sterically hindered substrates were successfully coupled in high yield using Pd(PPh(3))(4) or Pd(OAc)(2) with SPhos as the catalyst system.     

Nickel(II) complexes of bidentate N-heterocyclic carbene/phosphine ligands: efficient catalysts for Suzuki coupling of aryl chlorides

Nickel(II) complexes of bidentate N-heterocyclic carbene (NHC)/phosphane ligand L were prepared and structurally characterized. Unlike palladium, which forms [PdCl(2)(L)], the stable nickel product isolated is the ionic [Ni(L)(2)]Cl(2). These Ni(II) complexes are highly robust in air. Among different N-substituents on the ligand framework, the nickel complex of ligand L bearing N-1-naphthylmethyl groups (2 a) is a highly effective catalyst for Suzuki cross-coupling between phenylboronic acid and a range of aryl halides, including unreactive aryl chlorides. The activities of 2 a are largely superior to those of other reported nickel NHC complexes and their palladium counterparts. Unlike the previously reported [NiCl(2)(dppe)] (dppe=1,2-bis(diphenylphosphino)ethane), 2 a can effectively catalyze the cross-coupling reaction without the need for a catalytic amount of PPh(3), and this suggests that the PPh(2) functionality of hybrid NHC ligand L can partially take on the role of free PPh(3). However, for unreactive aryl chlorides at low catalyst loading, the presence of PPh(3) accelerates the reaction.