We report the efficient N-arylation of acyclic secondary amides and related nucleophiles with aryl nonaflates, triflates, chlorides. This method allows for easy variation aromatic component in tertiary amides. A new biaryl phosphine P-bound 3,5-(bis)trifluoromethylphenyl groups was found to be uniquely effective this amidation. The critical aspects ligand were explored through synthetic, mechanistic, computational studies. Systematic revealed importance (1) a methoxy group on carbon “top...

Abstract Simple Brønsted acids such as p ‐toluenesulfonic acid monohydrate (PTS) or polymer‐bound efficiently catalyze the direct nucleophilic substitution of hydroxy group allylic and benzylic alcohols with a large variety carbon‐ heteroatom‐centered nucleophiles. Reaction conditions are mild, process is conducted under an atmosphere air without need for dried solvents, water only side product reaction.

Simple Brønsted acids such as p-toluenesulfonic acid monohydrate (PTS) efficiently catalyze a direct substitution of the hydroxyl group in propargylic alcohols with 1,3-dicarbonyl compounds. Selective propargylation or allenylation is obtained depending on nature alkynol. Reactions can be performed air undried solvents water being only side product process. By applying this reaction key step, range interesting polysubstituted furans easily synthesized one-pot procedure. [reaction: see text].

Can you dig it? An asymmetric synthesis of functionalized 1H-indenes from easily available ortho-(alkynyl)styrene derivatives under mild reaction conditions has been achieved. The reactions proceed through an unprecedented and selective 5-endo-dig gold(I)-catalyzed cycloisomerization or alkoxycyclization, if water alcohol is present (see scheme). Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited...

The first asymmetric organocatalytic synthesis of helicenes is reported. A novel SPINOL-derived phosphoric acid, bearing extended π-substituents, catalyzes the through an enantioselective Fischer indole reaction. variety azahelicenes and diazahelicenes could be obtained with good to excellent yields enantioselectivities.

Strategic global industries, such as pharmaceutics, cosmetics, or crop production, are increasingly demanding high-value enantioenriched compounds. Thus, the design and development of efficient selective asymmetric catalysts undoubtedly required. To solve this situation, discovery innovative catalyst motifs, including unreported structural backbones activation modes, that able to overcome actual limitations is essential. This Review discloses mechanically interlocked molecules emerging...

Abstract Organic acids such as PTS efficiently catalyze direct nucleophilic substitutions of the hydroxy groups propargylic alcohols with a large variety carbon‐ and heteroatom‐centered nucleophiles. Reactions can be conducted under mild conditions in air without need for dried solvents. on multigram scales are also possible. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

The direct alkylation of 1,3-dicarbonyl compounds with benzylic alcohols is shown to be efficiently catalyzed by simple Brønsted acids such as triflic acid (TfOH) and p-toluenesulfonic (PTS) give rise monoalkylated dicarbonyl derivatives in high yields. In the absence nucleophile, substituted alkenes, generated through a formal dimerization reaction, are obtained. reactions carried out air using undried solvents, water being only side product process.

"Fisching" for complexity: The chiral Brønsted acid (R)-STRIP catalyzes the asymmetric Fischer indolization of a range monosubstituted cyclopentanones and cyclohexanones to give fused indolines bearing quaternary stereogenic center at 3-position. method has been extended include substrates tethered nucleophile, thus allowing enantioselective indolization/ring-closing cascades complex propellanes featuring two vicinal stereocenters.

The sulfur-based template of light-driven molecular shuttles is able to modulate its catalytic activity in a diastereoselective chalcogeno-Baylis–Hillman reaction.

The intramolecular cyclization of N-benzylfumaramide [2]rotaxanes is described. mechanical bond these substrates activates this transformation to proceed in high yields and a regio- diastereoselective manner, giving interlocked 3,4-disubstituted trans-azetidin-2-ones. This activation effect markedly differs from the more common shielding protection threaded functions by macrocycle, case promoting an unusual disfavored 4-exo-trig ring closure. Kinetic synthetic studies allowed us delineate...

Abstract Simple organic acids like 2,4‐dinitrobenzenesulfonic acid (DNBSA) catalyze the Ritter reaction of secondary benzylic alcohols giving rise to corresponding N ‐benzylacetamides in usually high yields. Reactions can be conducted without exclusion oxygen and need dry solvents. With tertiary α,α‐dimethylbenzylic a different pathway involving formal dimerization takes place under acid‐catalytic conditions used. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Immobilised Pd–NHC catalysts were successfully applied in Suzuki–Miyaura reaction under batch and flow conditions.

Abstract Es wird über die erste asymmetrische organokatalytische Synthese von Helicenen berichtet. Eine neue SPINOL‐abgeleitete Phosphorsäure mit ausgedehnten π‐Substituenten katalysiert eine enantioselektive Fischer‐Indolisierung. Vielzahl Azahelicenen und Diazahelicenen konnte auf diese Weise guten bis sehr Ausbeuten Enantioselektivitäten erhalten werden.

We have prepared a photoresponsive metal–organic framework by using an amide-based [2]rotaxane as linker and copper(II) ions metal nodes. The interlocked was obtained the hydrogen bond-directed approach employing fumaramide thread template of macrocyclic component, this latter incorporating two carboxyl groups. Single crystal X-ray diffraction analysis framework, under solvothermal conditions, showed formation stacked 2D rhombohedral grids forming channels decorated with alkenyl threads. A...

Fumaramide threads bearing one l-prolinamide fragment have been designed as templates for promoting the efficient formation of novel Leigh's [2]rotaxanes. Both and rotaxanes are shown to catalyze asymmetric addition ketones β-nitrostyrene in an enantio- diastereoselective manner. Interestingly, enantioselective course these processes is reversed simply by changing from thread rotaxane catalyst. DFT computations allowed rationalize stereodivergence interlocked noninterlocked catalysts.

The synthesis of chiral mechanically interlocked molecules has attracted a lot attention in the last few years, with applications different fields, such as asymmetric catalysis or sensing. Herein we describe orientational mechanostereoisomers, which include benzylic amide macrocycle stereogenic center, and nonsymmetric N-(arylmethyl)fumaramides axis. base-promoted cyclization initial fumaramide thread allows enantioenriched value-added compounds, lactams ring sizes amino acids, to be...

Abstract Direct alkylation of indoles with a wide variety tertiary propargylic alcohols under Brønsted acid catalysis conditions has been studied. A general and environmentally friendly method for the synthesis 3‐propargylated quaternary carbon atoms at their positions developed. The reactions are highly regioselective regard both to indole alkynol components. Only N ‐unsubstituted 2‐arylindoles do competitive S ′ take place afford 3‐dienyl‐ or 3‐allenylindoles, depending on moiety. were...

Highly substituted benzene derivatives have been easily prepared in a regioselective way from readily available 1,3-hexadien-5-ynes through gold(I)-catalyzed tandem reaction. The process involves an initial cyclization followed by selective Wagner-Meerwein shift which the migration preference seems to be determined ability stabilize positive charge.

Abstract Indenes and related polycyclic structures have been efficiently synthesized by gold(I)‐catalyzed cycloisomerizations of appropriate ortho ‐(alkynyl)styrenes. Disubstitution at the terminal position olefin was demonstrated to be essential obtain products originating from a formal 5 ‐endo ‐ dig cyclization. Interestingly, complete switch in selectivity cyclization o ‐(alkynyl)‐α‐methylstyrenes 6‐ endo 5‐ observed adding an alcohol reaction media. This allowed synthesis interesting...

The dethreading of a series succinamide-based [2]rotaxanes bearing benzylic amide macrocycles is reported herein. These transformations proceeded quantitatively either under flash vacuum pyrolysis, conventional heating, or microwave irradiation. Studying the size complementarity stoppers at ends thread and cavity macrocycle allowed us to set up best substituents for implementing extrusion from interlocked precursors. A variety 1H NMR kinetic experiments were carried out in order evaluate...

Abstract The synthesis of optically active interlocked and non‐interlocked 2‐azetidinones by intramolecular cyclization N ‐(α‐methyl)benzyl fumaramide [2]rotaxanes is described. Two different strategies asymmetric induction were tested in which the chiral group was located either proximal or distal to reacting center thread. During these experiments, an interesting equilibration process inside macrocyclic void occurred, thus leading through (α‐methyl)benzyl carbon atom giving rise β...