Porous organic polymers (POPs) containing catalytically active mononuclear metal centers can bridge the gap between homogeneous and heterogeneous catalysis. These materials offer catalysts with straightforward control over site analogously to organometallic catalysts; however, just like classical catalysts, they are easy separate from reaction mixtures recycle. The main objective of this Review is provide an overview different types reactions for synthetic chemistry where metal-POP have been...

A Au(I)-catalyzed hydroamination or hydration of 1,3-diynes to access 2,5-diamidopyrroles and 2,5-diamidofurans has been developed. This method can also be expanded 2,5-disubstituted furans 1,2,5-trisubstituted pyrroles including the formation deuterated heterocycles 18O-labeled furans.

Furans of gold: The first example a gold-catalyzed intermolecular addition carbon ylides to terminal alkynes is reported (see scheme; DCE=dichloroethane, Tf=trifluoromethanesulfonyl). Subsequent intramolecular trapping the generated gold carbene completes formal [3+2] cycloaddition, which represents novel synthesis 2,4-disubstituted furans. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset....

A highly regioselective hydroamination of unsymmetrical electron-poor and electron-rich alkynes with anilines catalyzed by Au(I) under mild conditions is reported. In addition, applications toward indole syntheses are presented including an example a one-pot synthesis from nonfunctionalized aniline.

Due in part to the common occurrence of five-membered nitrogen heterocycles bioactive molecules, discovery methods for enantioselective synthesis such structures is a useful endeavor. Building on single example by Tong phosphine-catalyzed [4 + 1] annulation an amine with allene that furnished achiral dihydropyrrole 22% yield, we have developed, aid new chiral spirophosphine catalyst, method increased utility, specifically, improved enhanced scope (the use γ-substituted allenes), and good ee....

A method for direct access to enantioenriched benzylic amides and carbamate-protected primary benzylamines by C-H functionalization is reported. The substrate used as limiting reagent with only a small excess of the unactivated amide or carbamate nucleophile. enantioselective intermolecular dehydrogenative C-N bond formation enabled combination chiral copper catalyst, photocatalyst, an oxidant, it takes place under mild conditions, which allow broad scope. compatible late-stage...

Abstract Aryl fluorides are important structural motifs in many pharmaceuticals. Although the Balz–Schiemann reaction provides an entry to aryl from aryldiazonium tetrafluoroborates, it suffers drawbacks such as long time, high temperature, toxic solvent, gas release, and low functional group tolerance. Here, we describe a general method for synthesis of tetrafluoroborates using piezoelectric material redox catalyst under ball milling conditions presence Selectfluor. This approach...

A gold mine of results: series ynamides have been dimerized in the presence a gold(I) complex. This unprecedented transformation involves formation key keteniminium intermediate that reacts to form variety cyclic and acyclic products. The substitution pattern ynamide determines which product is formed (see scheme; EWG=electron-withdrawing group, Ts=p-toluenesulfonyl).

A new SO2 surrogate is reported that cheap, bench-stable, and can be accessed in just two steps from bulk chemicals. Essentially complete release achieved 5 minutes. Eight established sulfonylation reactions proceeded smoothly by ex situ formation of utilizing a two-chamber system combination with the surrogate. Furthermore, we report first direct aminosulfonylation between aryl iodides amines. Broad functional group tolerance demonstrated, method applicable to pharmaceutically relevant...

A nickel-catalyzed cross-electrophile coupling reaction between (hetero)aryl bromides and 2,2-difluorovinyl tosylate is presented. This protocol provides facile incorporation of the gem-difluorovinyl moiety in organic molecules. The method features mild conditions, good functional group tolerance, excellent yields. Furthermore, mechanistic experiments DFT studies indicate a Ni(0)/Ni(II) catalytic cycle, thus differing from currently accepted cycle for C(sp2)–C(sp2) reactions.

A copper-catalyzed four-component enantioselective arylsulfonylcyanation of vinylarenes has been developed that enables easy access to a variety chiral β-sulfonyl nitriles with up 95% yield and 96% ee. The reaction utilizes bench-stable SO2 surrogate (SOgen), takes place under mild conditions, exhibits good substrate scope functional group compatibility. Control experiments show the use SOgen as is key achieving excellent reactivities enantioselectivities. Preliminary mechanistic data...

In the presence of a Cu(I) catalyst and pyridine oxide, alkynyl oxiranes oxetanes can be converted into functionalized five- or six-membered α,β-unsaturated lactones dihydrofuranaldehydes. This new oxidative cyclization is proposed to proceed via an unusual allenyloxypyridinium intermediate.

Ringschluss mit Gold: Die erste Gold-katalysierte intermolekulare Addition von Kohlenstoff-Yliden an terminale Alkine wird beschrieben (siehe Schema; DCE=Dichlorethan, Tf=Trifluormethansulfonyl). Anschließendes intramolekulares Abfangen des erzeugten Goldcarbens vervollständigt eine formale [3+2]-Cycloaddition in einer neuartigen Synthese 2,4-disubstituierten Furanen.

A light-induced redox-neutral Ni-catalyzed sp3 C–H alkylation of unactivated alkenes with alkyl bromides possessing β-hydrogens is described herein. The method distinguished by its simplicity, wide scope, and exquisite regio- chemoselectivity profile, thus offering an entry point to forge sp3–sp3 architectures.

Efficient synthesis of sulfonamides has long been pursued by chemists due to their frequent occurrence in pharmaceuticals, especially anti-inflammatory medicines. The traditional assembly from sulfonyl chlorides and amines, as well the recently developed one-step involving sulfur dioxide, still faces challenges such poor substrate compatibility and/or stringent reaction conditions. Herein, we present a strategy for situ generation sulfamoyl radicals modular both alkenyl alkyl with wide...

Abstract Herein, we disclose a simple copper‐catalyzed method for enantioselective allylic C(sp 3 )−H oxidation of unsymmetrical acyclic alkenes, specifically 1‐aryl‐2‐alkyl alkenes. The C−H substrates are used in limiting amounts, and the products obtained with high enantioselectivity, E / Z ‐selectivity, regioselectivity. exhibits broad functional group tolerance, ‐alkene mixtures suitable substrates. transformation is enabled by light irradiation, which sustains copper catalysis...

Abstract A new synthetic route to the privileged 1,2‐dihydroisoquinolines is reported. This method, which relies on a gold‐catalyzed formal [4+2] cycloaddition between ynamides and imines, provides retrosynthetic disconnection of 1,2‐dihydroisoquinoline core by installing 1,8a CC 2,3 CN bonds in one step. Both aldimines ketimines can be used as substrates. In addition, example dihydrofuropyridine synthesis also demonstrated.

Synthesis of biaryl motifs are crucial for the development and synthesis pharmaceuticals, natural products, functional materials. During last decade, gold-catalyzed aryl–aryl coupling reactions have evolved from a curiosity to well-established research field. This review summarizes field early examples up latest developments. Facile C–H functionalization orthogonal reactivity compared many other types transition metal catalysis, example, palladium makes highly appealing valuable. 1...

A copper-catalyzed route to α-substituted, primary benzylamines by C–H functionalization of alkylarenes is described. The method directly affords the amine hydrochloride salt. Catalyst loadings down 0.1 mol % in combination with scalability, insensitivity air and moisture, no need for column chromatography makes procedure highly practical. facile synthesis racemate a blockbuster drug highlights relevance development pharmaceuticals. Preliminary mechanistic data are also included.

A series of chiral spiroketal bisphosphine ligands containing 1,1'-spirobi(3 H,3' H)isobenzofuran backbones was accessed through asymmetric synthesis and subsequently tested in enantioselective Rh-catalyzed hydrogenation α-dehydroamino acid esters. The ligand providing the highest enantioselectivity (up to 99.5%) obtained seven steps an overall 38% yield. could be performed on a gram scale, no kinetic resolution enantiomers is required. Overall, developed provides easily accessible...

The silylative pinacol coupling of arylaldehydes catalyzed by an easily accessible, heterogeneous base-metal catalyst is demonstrated. Instead using the classical combination catalyst, stoichiometric metal reductants, and chlorosilanes, developed reaction only requires use a hydrosilane, which serves as both reductant silylating agent. A rare mechanistic investigation in this field focusing on organic reactants was undertaken various techniques including experimental rate orders, kinetic...