RESUMO
Regiodivergent palladium-catalyzed alkene difunctionalization reactions between diethyl malonate and 1,5-dienes bearing a triflate group at C2 are described. Use of tris(2,4-di-tert-butylphenyl)phosphite as a ligand leads to 4-exo-cyclization/functionalization to afford malonate-substituted methylene cyclobutanes. In contrast, the 1,2-bis(diphenylphosphino)benzene ligand provides methylene cyclopentanes via 5-endo-cyclization/functionalization. The five-membered ring-forming reactions occur via anti-carbopalladation of the enolate nucleophile, whereas four-membered ring-forming reactions proceed through syn-4-exo-migratory insertion of the tethered alkene, followed by C(sp3)-C(sp3) bond-forming reductive elimination from an (alkyl)Pd(II)(malonate) complex.
Assuntos
Ciclobutanos , Paládio , Alcenos , Ciclopentanos , Ligantes , Catálise , MalonatosRESUMO
A palladium-catalyzed cross-coupling of thioacetates and aryl halides is described herein. Using a catalyst screening kit, tBuBrettPhos Pd G3 was found to be a unique catalyst for this reaction, affording the desired thioarene products in high yields under mild reaction conditions. The thioacetate starting materials are readily available, allowing for quick access to these more lab friendly reagents. Reactions described herein range from the late-stage coupling of complex thioacetates to the first report of a mild set of conditions for thiomethylation of aryl halides.
RESUMO
Over the past few years our group has described a new type of alkene difunctionalization reaction in which aryl or alkenyl triflates bearing tethered alkenes are coupled with various nucleophiles to afford carbocyclic products. The products are formed in moderate to good chemical yield, with generally high levels of stereoselectivity. Our progress to date in this area, which includes reactions of amine, alcohol, enolate, and indole nucleophiles, is described in this review.
RESUMO
The Pd-catalyzed coupling of malonate nucleophiles with alkenes bearing tethered aryl or alkenyl triflates is described. These alkene difunctionalization reactions afford malonate-substituted cyclopentanes that contain fused aryl or cycloalkenyl rings. The transformations generate a five-membered ring, two C-C bonds, and provide products bearing up to three stereocenters with good chemical yield and generally high diastereoselectivity.
Assuntos
Alcenos/química , Ciclopentanos/síntese química , Paládio/química , Alquilação , Aminação , Catálise , Ciclopentanos/química , Malonatos , Estrutura MolecularRESUMO
Palladium-catalyzed alkene difunctionalization reactions between alkenes bearing tethered aryl or alkenyl triflates and enolate nucleophiles are described. The transformations form two C-C bonds, a ring, and up to two stereocenters, while producing substituted cyclopentane derivatives that contain appended carbonyl functionality. Products are formed with up to >20:1 diastereoselectivity, and formation of sterically congested bonds between quaternary carbon atoms is feasible.
RESUMO
This review summarizes recent developments in palladium-catalyzed alkene carboalkoxylation and carboamination reactions. New synthetic methods that have been reported in the past four years are described, along with mechanistic issues and the influence of mechanism on product stereochemistry. The applications of these transformations to the synthesis of natural products and other biologically relevant compounds are also discussed.
RESUMO
Intermolecular alkene difunctionalization reactions between terminal alkenes bearing a pendant aryl or alkenyl triflate electrophile and exogenous alcohol or phenol nucleophiles are described. These transformations afford substituted indanyl or alkylidenecyclopentyl ethers in high yield with excellent diastereoselectivity. The transformations proceed through intermolecular capture of an intermediate [Pd(II)-alkene]+[OTf]- complex by the alcohol or phenol nucleophile.
RESUMO
Amino-substituted alkylidenecyclopentanes were synthesized through a stereoselective intermolecular Pd-catalyzed alkene carboamination reaction between alkenyl triflates bearing a pendant alkene and exogenous amine nucleophiles. The reactions are effective with a range of different substrate combinations, and proceed with generally high diastereoselectivity. Use of (S)-tBuPhox as the ligand in reactions of achiral substrates provides enantioenriched products with up to 98.5:1.5â e.r.
RESUMO
A new type of Pd-catalyzed alkene carboamination reaction that provides direct access to enantioenriched 2-aminoindanes from 2-allylphenyltriflate derivatives and aliphatic amines is described. A catalyst generated in situ from Pd(OAc)2 and (S)-tert-butylPHOX provides the functionalized carbocycles in good yield with up to >99:1 er. The transformations occur via a key anti-aminopalladation that involves intermolecular attack of an amine nucleophile on an arylpalladium alkene complex.
Assuntos
Alcenos/química , Indanos/química , Indanos/síntese química , Paládio/química , Aminação , Catálise , Técnicas de Química SintéticaRESUMO
Cascade Pd-catalyzed alkene carboamination/Diels-Alder reactions between bromodienes and amines bearing two pendant alkenes are described. These transformations generate 4 bonds, 3 rings, and 3-5 stereocenters to afford polycyclic nitrogen heterocycles with high diastereoselectivity.