Recyclable Copper(I)-Catalyzed Cross-Coupling of Trialkylsilylethynes and N-Tosylhydrazones Leading to the Formation of C(sp)-C(sp3) Bonds.

A highly efficient heterogeneous copper(I)-catalyzed cross-coupling of trialkylsilylethynes with N-tosylhydrazones has been achieved in dioxane at 90-110 °C via the Cu carbene migratory insertion with an SBA-15-immobilized l-proline-Cu(I) complex [SBA-15-l-Proline-CuI] as the catalyst and LiOtBu as the base, leading to the formation of C(sp)-C(sp3) bonds. The reaction generates a wide variety of alkyltrialkylsilylalkynes in moderate to high yields. This new heterogenized copper(I) complex exhibits a comparable catalytic efficiency to homogeneous CuI and can be easily recovered through a simple centrifugation process and is recyclable up to 12 times without a remarkable loss of activity.

Recyclable gold(I)-catalyzed heterocyclization of ynamides with benzyl or indolyl azides towards 2-aminoindoles or 3-amino-ß-carbolines.

A highly efficient heterogeneous gold(I)-catalyzed heterocyclization of ynamides with benzyl or indolyl azides has been achieved in 1,2-dichloroethane under mild conditions via a heterogenized α-imino gold carbene intermediate using 5 mol% of SBA-15-anchored strongly hindered NHC-gold(I) complex [IPr-SBA-15-AuNTf2] as the catalyst, delivering a wide range of valuable 2-aminoindoles or 3-amino-ß-carbolines in mostly good to excellent yields with high regioselectivity. Furthermore, the new heterogenized NHC-gold(I) complex displays the same catalytic activity as IPrAuNTf2 and is facile to recover by centrifugation of the reaction mixture and can be reused at least seven times without any appreciable drop in its catalytic activity.

Regio- and Diastereoselective Construction of Functionalized Benzo[b]oxepines and Benzo[b]azepines via Recyclable Gold(I)-Catalyzed Cyclizations.

The heterogeneous gold-catalyzed cyclization of (o-alkynyl)phenoxy- or N-(o-alkynylphenyl)tolylsulfonamidoacrylates with alcohols has been developed by using an MCM-41-anchored diphenylphosphine-Au(I) complex [MCM-41-Ph2P-AuNTf2] as the catalyst under mild reaction conditions, yielding diverse functionalized benzo[b]oxepines or benzo[b]azepines with good to high yields and excellent diastereoselectivity. This heterogenized gold(I) catalyst exhibits a comparable activity to homogeneous Ph3PAuNTf2 and can be facilely recovered by a simple filtration of the reaction solution and reused more than seven times with almost a consistent catalytic efficiency.

Recyclable Gold Catalyst for the Stereoselective Thioallylation of Alkynes.

The heterogeneous gold(I)-catalyzed stereoselective thioallylation of electron-deficient alkynes with allyl sulfides has been achieved by using an MCM-41-immobilized sterically demanding NHC-gold(I) complex [MCM-41-IPrAuNTf2] as the catalyst under mild conditions, delivering a wide variety of stereodefined tri- and tetrasubstituted functionalized vinyl sulfides in good to excellent yields. The new heterogeneous MCM-41-IPrAuNTf2 catalyst exhibits an activity comparable to a homogeneous IPrAuNTf2 complex and can be recovered via a simple filtration process and reused for at least seven consecutive cycles without any apparent loss of its catalytic activity and selectivity.

Recyclable Heterogeneous Palladium-Catalyzed Cyclocarbonylation of 2-Iodoanilines with Acyl Chlorides in the Biomass-Derived Solvent 2-Methyltetrahydrofuran.

A highly efficient, green palladium-catalyzed cyclocarbonylation of 2-iodoanilines with acyl chlorides has been developed that proceeds smoothly in a biomass-derived solvent 2-methyltetrahydrofuran with N,N-diisopropylethylamine as base at 100 °C under 20 bar of carbon monoxide using an 2-aminoethylamino-modified MCM-41-anchored palladium acetate complex [2N-MCM-41-Pd(OAc)2] as a heterogeneous catalyst, yielding a wide variety of 2-substituted 4H-3,1-benzoxazin-4-one derivatives in good to excellent yields. This supported palladium catalyst could be facilely obtained by a two-step procedure from easily available starting materials and readily recovered via a simple filtration process and recycled at least 8 times without any apparent decrease in catalytic efficiency. The developed methodology not only avoids the use of toxic solvents such as tetrahydrofuran and dimethylformamide but also solves the basic problem of expensive palladium catalyst recovery and reuse and prevents effectively palladium contamination of the desired product.

A Heterogeneous Gold(I)-Catalyzed [2 + 2 + 1] Annulation of Terminal Alkynes, Nitriles, and Oxygen Atoms Leading to 2,5-Disubstituted Oxazoles.

The first heterogeneous gold(I)-catalyzed [2 + 2 + 1] annulation of terminal alkynes, nitriles, and oxygen atoms has been achieved by using an MCM-41-immobilized phosphine-gold(I) complex as catalyst and 8-methylquinoline N-oxide as oxidant under mild conditions, yielding a variety of 2,5-disubstituted oxazoles in good to excellent yields with broad substrate scope. The new heterogeneous gold(I) catalyst can easily be recovered by simple filtration of the reaction solution and recycled for at least eight times without significant loss of activity.

Phosphine-Free, Heterogeneous Palladium-Catalyzed Atom-Efficient Carbonylative Cross-Coupling of Triarylbismuths with Aryl Iodides: Synthesis of Biaryl Ketones.

A novel and highly efficient heterogeneous palladium-catalyzed carbonylative cross-coupling of aryl iodides with triarylbismuths has been developed that proceeds smoothly at atmospheric CO pressure and provides a general and powerful tool for the preparation of various valuable biaryl ketones with high atom economy, good to excellent yield, and recyclability of the catalyst. The reaction is the first example of Pd-catalyzed carbonylative cross-coupling for the construction of biaryl ketones using triarylbismuths as substrates.

Recyclable and Reusable [RuCl2(p-cymene)]2/Cu(OAc)2/PEG-400/H2O System for Oxidative C-H Bond Alkenylations: Green Synthesis of Phthalides.

[RuCl2(p-cymene)]2 in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be an extremely efficient catalyst for the cross-dehydrogenative C-H bond alkenylation reaction between benzoic acids and alkenes. The reaction could be conducted at 80 °C using Cu(OAc)2·H2O as oxidant, yielding a variety of phthalide derivatives in good to excellent yields. More importantly, both [RuCl2(p-cymene)]2 and Cu(OAc)2 in the PEG-400/H2O system could be easily recycled and reused six times without any loss of catalytic activity.

Synthesis of indolyl imidazole derivatives via base-promoted tandem reaction of N-[2-(1-alkynyl)phenyl]carbodiimides with isocyanides.

An efficient route to indolyl imidazole derivatives has been developed through a base-promoted tandem reaction of N-[2-(1-alkynyl)phenyl]carbodiimides with isocyanides in DMSO at 40 °C. The present tandem process allows the assembly of a variety of indolyl imidazole derivatives in moderate to good yields.

An MCM-41-immobilized dichloro(pyridine-2-carboxylato)gold(III) complex: an efficient and recyclable catalyst for the annulation of anthranils and ynamides.

A new mesoporous MCM-41-immobilized dichloro(pyridine-2-carboxylato)gold(III) complex [MCM-41-PicAuCl2] was synthesized via an addition reaction of a dichloro(3-hydroxypyridine-2-carboxylato)gold(III) complex to triethoxy(3-isocyanatopropyl)silane, followed by immobilization on MCM-41 and was characterized by different physico-chemical techniques. In the presence of 5 mol% of MCM-41-PicAuCl2, the annulation reaction between anthranils and ynamides proceeded smoothly under mild conditions to afford diverse 6- or 5-formylindoles with high atom economy and good to excellent yields. This new heterogenized gold(III) complex can be easily recovered through a simple filtration process and recycled more than seven times without any apparent loss of its catalytic efficiency.

Heterogeneous gold-catalyzed Sandmeyer coupling of aryldiazonium salts with sodium bromide or thiols for constructing C-Br and C-S bonds.

An efficient heterogeneous gold-catalyzed Sandmeyer coupling of aryldiazonium salts with sodium bromide or thiols for the formation of C-Br and C-S bonds has been achieved in high yields and selectivities under mild conditions by using a bis(diphenylphosphinomethyl)amino-modified mesoporous MCM-41-immobilized gold(I) chloride complex [MCM-41-2Ph2PAuCl] as the catalyst without using sacrificial oxidants. Vital to the success of this C-heteroatom coupling is the nucleophile-promoted activation of aryldiazonium salts, which can serve as an efficient oxidant for the conversion of Au(I) to Au(III) without the use of a photocatalyst or an assisting ligand. This new heterogenized gold(I) complex can be easily prepared by a simple procedure and recovered via centrifugation, and recycled more than seven times without any significant loss of its catalytic efficiency.

Recyclable heterogeneous gold(I)-catalyzed oxidative ring expansion of alkynyl quinols: a practical access to tropone and its analogues.

The heterogeneous gold(i)-catalyzed oxidative ring expansion of alkynyl quinols has been achieved by using a benzyldiphenylphosphine-modified MCM-41-immobilized gold(i) complex [MCM-41-BnPh2P-AuNTf2] as the catalyst and 8-methylquinoline N-oxide as the oxidant under mild reaction conditions, yielding a variety of functionalized tropone derivatives in good to excellent yields. Extension of this methodology allows for facile construction of other seven- or six-membered ring systems including dibenzotropones, dibenzooxepines, phenanthrenes, and quinolin-2(1H)-ones. This new heterogeneous gold(i) complex can be readily recovered through a simple filtration process and recycled at least eight times without any apparent decrease in catalytic efficiency.

Ruthenium(III) chloride catalyzed acylation of alcohols, phenols, and thiols in room temperature ionic liquids.

Ruthenium(III) chloride-catalyzed acylation of a variety of alcohols, phenols, and thiols was achieved in high yields under mild conditions (room temperature) in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF(6)]). The ionic liquid and ruthenium catalyst can be recycled at least 10 times. Our system not only solves the basic problem of ruthenium catalyst reuse, but also avoids the use of volatile acetonitrile as solvent.

The copper(I)-catalyzed tandem reaction of o-alkynylphenyl isothiocyanates with isocyanides: a rapid synthesis of 5H-benzo[d]imidazo[5,1-b][1,3]thiazines.

An efficient route to 5H-benzo[d]imidazo[5,1-b][1,3]thiazines has been developed using the copper(i)-catalyzed tandem reaction of o-alkynylphenyl isothiocyanates with isocyanides in THF with Cs2CO3 as base. The present tandem process allows the assembly of a variety of 5H-benzo[d]imidazo[5,1-b][1,3]thiazines in good to excellent yields.