Xiangge Zhou

An Efficient Copper-Catalyzed Carbon−Sulfur Bond Formation Protocol in Water

An efficient protocol of copper-catalyzed C-S bond formation between aryl halides and potassium thiocyanate leading to diaryl sulfides is reported. A variety of diaryl sulfides can be synthesized in good to excellent yields up to 94%.

Cu-catalyzed three-component synthesis of substituted benzothiazoles in water.

Three in one: Copper-catalyzed three-component reactions, involving 2-iodoanilines, aldehydes, and sulfur powder, afford 2-phenylbenzothiazoles in water. A variety of 2-substituted benzothiazoles can be obtained in good to excellent yields of up to 96 % (see scheme).

A Simple and Efficient Catalytic System for N-Arylation of Imidazoles in Water

N-Aryl imidazoles are key structural motifs in a wide range of agrochemicals, pharmaceuticals, and biologically active compounds and have been exploited as important precursors of versatile N-heterocyclic carbenes, a powerful class of ligands for transition-metal catalysis or room-temperature ionic liquids. A traditional method of introducing this functionality is nucleophilic aromatic substitution of imidazole with activated aryl halides (SNAr reactions) or classic Ullmann-type coupling reactions. However, these well-known methods suffer from several drawbacks, such as high reaction temperature, stiochiometric amounts of metal reagents, and low functional-group tolerance, which has limited their applications. Recently, Buchwald et al. and Taillefer et al. found several Nand O-based ligands could greatly facilitate the copper-catalyzed path for the N-arylation of imidazoles. After the discovery of these ligands, ACHTUNGTRENNUNGinterest in this field has increased spectacularly in the last few years and resulted in the golden age of copper-catalyzed Ullmann-type coupling reactions. While many important results have been achieved via this methodology, it is worth noting that these protocols are generally operated in volatile organic solvents with transitionmetal ions. From the standpoint of green chemistry, the development of more environmentally benign reaction media, such as water, in place of organic solvents would be desirable. Henceforth, as part of our endeavors toward the development of environmentally friendly protocols, efforts were directed towards performing the N-arylation reaction by using water as the sole reaction medium. To date, salen ligands have been recognized as one of the most efficient auxiliaries, and many metallosalen complexes are used as excellent catalysts in various organic transformations. Herein we report the first example the N-arylation of imidazoles directly catalyzed by sulfonato–CuACHTUNGTRENNUNG(salen) complex 1 under mild conditions in water with satisfactory results. This catalytic system contains several advantages: 1) Water, a green solvent, is used in place of volatile organic solvents; 2) the catalysis reactions could be performed without an inert gas atmosphere and with low catalyst loading; 3) the work-up procedure is simple with excellent yields; 4) the catalyst could be easily recovered and used again. As shown in Scheme 1, catalyst 1 could be conveniently synthesized in 82 % yield by a one-pot reaction of three

Ratiometric fluorescent pH probes based on aggregation-induced emission-active salicylaldehyde azines

A series of luminescent salicylaldehyde azines (SAs) containing different electron-accepting substituents (–NO2, –F, and –Cl), electron-donating substituents (–OMe and –NEt2), and a π-extended system (naphthalene ring) are prepared for the application of fluorescent pH probes. These SAs inheriting the aggregation-induced emission (AIE) features display strong blue, green, and red fluorescence with large Stokes shifts in water and solid medium. Combining the advantages of AIE and the chemical reactivity of phenol towards OH−/H+, most of the SAs can be used as ratiometric fluorescent pH probes with a broad pH range (2–14) in water and solid medium (test paper). Moreover, the inherent relationship between their chemical structures and AIE properties/pKa values (7.5–13.3) is studied, which provides unequivocal insights into the design of AIE-active dyes and their applications.

Synthesis and photophysical properties of water-soluble sulfonato-Salen-type Schiff bases and their applications of fluorescence sensors for Cu2+ in water and living cells

A series of water-soluble sulfonato-Salen-type ligands derived from different diamines including 1,2-ethylenediamine (Et-1-Et-4), 1,2-cyclohexanediamine (Cy-1 and Cy-2), 1,2-phenylenediamine (Ph-1-Ph-3 and PhMe-1-PhMe-4), and dicyano-1,2-ethenediamine (CN-1) has been designed and prepared. Sulfonate groups of ligands ensure good stability and solubility in water without affecting their excited state properties. These ligands exhibit strong UV/Vis-absorption and blue, green, or orange fluorescence. Time-dependent-density functional theory calculations have been undertaken to reveal the influence of ligand nature, especially sulfonate groups, on the frontier molecular orbitals. Since their fluorescence is selectively quenched by Cu(2+), the sulfonato-Salen-type ligands can be used as highly selective and sensitive turn-off fluorescence sensors for the detection of Cu(2+) in water and fluorescence imaging in living cells.

Highly Enantioselective Michael Addition of Malononitrile to Vinylogous Imine Intermediates Generated in situ from Arylsulfonyl Indoles

The conjugate addition of carbon-based nucleophiles to activated unsaturated systems represents one of the best established and most versatile carbon–carbon bond-forming reactions in organic chemistry. Malononitrile, a classic equivalent of a 1,3-dicarbonyl compound, might be a valuACHTUNGTRENNUNGable nucleophile, which can then be conveniently transformed into carboxylic acid, ester, amine, or amide groups. However, to the best of our knowledge, few studies of asymmetric Michael additions that use malononitrile as the nucleophile have been reported. Arylsulfonyl indoles 1, which bear a good leaving group, are an effective precursor for vinylogous imine intermedi-

Synthesis of 3-indole derivatives by copper sulfonato Salen catalyzed three-component reactions in water

An efficient three-component reaction of indole, aldehyde, and malononitrile in water catalyzed by a copper(II) sulfonato Salen complex afforded 3-indole derivatives in good to excellent yields up to 97%.

Palladium-Catalyzed CH ortho Arylation of Benzoic Acids with Diaryliodonium Salts in Water

Palladium-catalyzed C C bond-formation reactions between aryl halides or triflates and organometallic reagents are among the most useful methods to construct biaryls, which are usually structural motifs found in important nature products, pharmaceuticals, and organic materials. The corresponding organometallic nucleophilic starting materials, however, are often not commercially available and sometimes lead to the formation of undesired side products. Over the past decade, extensive efforts have been made to explore the transition-metal-catalyzed direct arylation of C H bonds as ecologically and economically friendly alternatives. Furthermore, owing to the requirement of site selectivity, directing groups such as pyridyl, acylamino, hydroxy, and phenolic ester groups have been broadly introduced into substrates. The majority of these directing groups cannot be easily removed from the products, and a few of them have to be deprotected by further transformations. In recent years, transition-metal-catalyzed decarboxylative coupling reactions have emerged as a powerful strategy to form carbon–carbon and carbon–heteroatom bonds from cheap, diverse, and readily available aryl carboxylic acids. The carboxylic acid group can efficiently be removed or converted into a variety of useful functional groups, which makes the directed ortho C H functionalization of carboxylic acids exceptionally practical for applications in organic synthesis. In 2007, the groups of Yu and Daugulis pioneered the direct ortho-arylation of benzoic acids with aryl halides by using palladium as a catalyst (Scheme 1 a). Also, Yu and co-workers demonstrated that phenylboronic acid esters and aryltrifluoroborates can be utilized as coupling partners for the ortho functionalization of benzoic acids (Scheme 1 b). 7] Recent work has identified that diaryliodonium salts, which are commercially available or easily synthesized, are important alternatives that can be used as arylation reagents in palladium-catalyzed C H arylation reactions. However, application of diaryliodonium salts in the catalytic ortho-arylation of benzoic acids has not yet been reported. The use of water as an environmentally benign, nonflammable, and nontoxic medium for organic transformations is strongly desired because of green chemistry. 10] As part of our continuous interest in aqueous catalysis, herein we report an efficient and practical protocol for the palladium-catalyzed C H ortho arylation of benzoic acids with diaryliodonium salts by using water as the solvent (Scheme 1 c). In our initial optimization study, m-toluic acid and phenyl(2,4,6-trimethylphenyl)iodonium triflate (2 a) were chosen as model substrates. As illustrated in Table 1, no desired product was found in the absence of catalyst by using water as the solvent (Table 1, entry 1). Gratifyingly, the substrates could be transformed into desired ortho-arylated product 3 a in 85 % yield by using a catalytic amount of Pd(OAc)2 (Table 1, entry 2). Next, a variety of organic solvents were tested; nevertheless, only a trace amount of the product was formed (Table 1, entries 3–10). The results suggest strongly that the choice of water as the solvent is crucial for this reaction. Replacing Pd(OAc)2 by PdCl2 resulted in a slightly lower yield of the product (78 %; Table 1, entry 11). Furthermore, low temperatures decelerated the reaction rate; product 3 a was obtained in 54 % yield if the reaction was performed at 80 8C (Table 1, entry 12). A symmetrical iodonium salt was also compatible with the reaction, and it provided a similar result (Table 1, entry 13). Scheme 1. Palladium-catalyzed C H ortho arylation of benzoic acids. Ac = acetyl, BQ = 1,4-benzoquinone, Mes = 2,4,6-trimethylphenyl, Tf = trifluoromethanesulfonyl.

Simple, selective, and sensitive colorimetric and ratiometric fluorescence/phosphorescence probes for platinum( ii ) based on Salen-type Schiff bases

Ratiometric fluorescence/phosphorescence probes for Pt2+ based on the fluorescence quenching from the ligand of Salen-type Schiff bases and phosphorescence enhancement from the resulting Pt(II) complexes have been demonstrated. For phosphorescence enhancement, a good linearity (correlation coefficient R2 = 0.996, n = 10) was established with detection limit of 11.6 ± 0.2 ppb. The detection limit would be decreased to 2.31 ± 0.03 ppb if degassing was adopted. To the best of our knowledge, this value is one of the most sensitive probes for Pt2+. This system also has good selectivity with little interference from Sr2+, Sn2+, Pb2+, Cr3+, Mn2+, Al3+, Fe3+, Ce3+, Ag+, Li+, Mg2+, Na+, Cd2+, Cu2+, Ca2+, Zn2+, K+, Co2+, Ni2+, Au3+, Ir3+, and Pd2+. Moreover, this system is suitable for detection of different Pt(II) sources, such as PtCl2, K2PtCl4, Pt(COD)Cl2 (COD = 1,5-cyclooctadiene), and cis-platin. It potentially provides a new and simple way to detect some useful transition metal ions, such as Cu+, Au+, Pd2+, and Ru2+.

Copper-catalyzed formation of N,N-dimethyl benzamide from nitrile and DMF under an O2 atmosphere

Amidation of nitrile with N,N-dimethylformamide (DMF) was catalyzed by Cu2O with 1,10-phenanthroline as a ligand under an oxygen atmosphere. A variety of N,N-dimethyl benzamides were obtained in yields up to 84%.