Copper-catalyzed olefinic trifluoromethylation and oxytrifluoromethylation of enamides is reported. The direct C–H constitutes an efficient method for the stereoselective synthesis β-trifluoromethyl substituted enamides.

Abstract Fluoroalkenes represent a class of privileged structural motifs, which found widespread use in medicinal chemistry. However, the synthetic access to fluoroalkenes was much underdeveloped with previous reported methods suffering from either low step economy or harsh reaction conditions. Here we present Rh III -catalysed tandem C–H/C–F activation for synthesis (hetero)arylated monofluoroalkenes. The readily available gem -difluoroalkenes as electrophiles provides highly efficient and...

Abstract The rhodium(III)‐catalyzed ortho CH alkynylation of non‐electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis functionalized alkynes represents first example merging hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates variety functional groups, more importantly, exhibits high selectivity monoalkynylation.

Chemoselective functionalizations of intrinsically less reactive C(sp3)–H bonds alkyl nitriles are particular interest to the chemical community because these strategies provide opportunities for introduction important cyanoalkyl groups onto target frameworks in a step-economical fashion. In recent years, nitrile-containing radicals tandem radical additions and oxidative couplings has inarguably brought chemists new reaction platform diverse synthesis natural products pharmaceuticals....

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFirst application of attractive intramolecular interactions to the design chiral catalysts for highly enantioselective Diels-Alder reactionsE. J. Corey and Teck Peng LohCite this: Am. Chem. Soc. 1991, 113, 23, 8966–8967Publication Date (Print):November 1, 1991Publication History Published online1 May 2002Published inissue 1 November 1991https://pubs.acs.org/doi/10.1021/ja00023a066https://doi.org/10.1021/ja00023a066research-articleACS...

It does get in! A fluoride-assisted direct cross-coupling of cyclic enamides with trialkoxy aryl silanes by a palladium-catalyzed C--H activation leads to wide range in yields up 95 %.

An efficient methodology for oxidative cross-coupling reaction of olefins with acrylates catalyzed by palladium(II) was developed. The corresponding dienoates were obtained in moderate to good yields.

A methyl sulfonyl radical generated from DMSO in the presence of catalytic Cu(<sc>i</sc>) under O₂atmosphere is used to carry out sulfonation C–C unsaturated bonds afford β-keto sulfones and (<italic>E</italic>)-vinyl sulfones.

This paper describes a palladium-catalyzed oxime assisted intramolecular dioxygenation of alkenes by using 1 atm air as the sole oxidant under extremely mild conditions, which demonstrated feasibility incorporating atmospheric oxygen into synthetically useful products at room temperature.

A Ru-catalyzed direct oxidative cross-coupling reaction of acrylates was developed. It offers a straightforward and atom-economical protocol for the synthesis functionalized (Z,E)-muconate derivatives in moderate to good yields with stereo- chemoselectivities. The conjugated muconates bearing differentiable terminal functionality can be selectively transformed into versatile synthetic intermediates widely used organic synthesis.

Diverse and controllable pathways induced by palladium-catalyzed intramolecular Heck reaction of N-vinylacetamides for the synthesis nitrogen-containing products in reasonable to high yields via tuning phosphine ligands bases are reported. Domino reactions including unique β-N-Pd elimination, 1,4-Pd migration, or direct acyl C-H bond functionalization were found be involved forming different products, respectively. Given ability using same starting material generate diverse completely...

Assistance provided: The directing group in the title reaction not only activates substrates but also allows stereospecific formation of cis-trifluoromethylated products. is operationally simple and tolerates a wide variety functional groups, thus providing an efficient method for stereoselective synthesis β-CF3-functionalized acrylamide derivatives. As service to our authors readers, this journal provides supporting information supplied by authors. Such materials are peer reviewed may be...

A six-membered cyclic vinylpalladium complex was synthesized via alkenyl C–H bond direct palladation, which probed in detail by 1H NMR spectroscopy and characterized X-ray analysis. The propounded to be the intermediate during olefination reaction of enamides. An efficient catalytic system for oxidative cross-coupling enamides with electron-deficient olefins catalyzed palladium(II) acetate 1 atm oxygen as sole oxidant developed. corresponding products were obtained moderate good yields under...

Using α,α-difluoromethylene alkyne as a nontraditional one-carbon reaction partner, synthetically novel method for the construction of isoindolin-1-one derivatives via Rh(III)-catalyzed [4+1] annulation is reported. The 2-fold C-F bond cleavage not only enables generation desired product under an overall oxidant-free condition but also results in net migration carbon-carbon triple bond. In addition, present protocol exhibits tolerance wide spectrum functional groups due to mild conditions employed.

A general Pd-catalyzed intermolecular reductive Heck reaction of both terminal and internal unactivated aliphatic alkenes has been first developed. This method affords γ- δ-arylated alkyl carboxylic acid derivatives in high yields with complete anti-Markovnikov selectivity. Notably, the coupling process is stereoretentive for chain. Mechanistically, palladacycle intermediates stabilized by directing group ligand, hydride species multigenerated from PS/TFA reductant, are two key factors that...

Rh(<sc>iii</sc>)-catalyzed C–H olefinic alkynylation of enamides for the stereospecific construction synthetically useful <italic>Z</italic>-type enynamides is reported. This protocol displays good functionality tolerance and operational simplicity thus providing an alternative synthetic opportunity ease access to specific 1,3-enyne derivatives.

A highly regioselective synthesis of branched vinylsilanes through silicon-copper additions to terminal alkynes catalyzed by copper(I) was developed using methanol as additive. The corresponding were obtained with excellent linear selectivity up 99/1 in good yields.

An iron-catalyzed carbodi- and trichloromethylation of activated alkenes with readily available dichloro- tetrachloromethane has been developed. A diaryliodonium salt is used as an efficient oxidant in this transformation. This reaction tolerates a variety functional groups allows for highly synthesis various chloro-containing oxindoles.

Copper-catalyzed highly efficient hydrosilylation reaction of enynoates was developed. Under simple conditions, various di-, tri-, and tetrasubstituted racemic allene products could be obtained in high yields. The asymmetric 1,6-addition silyl group to the (Z)-2-alken-4-ynoates achieved under mild conditions afford silyl-substituted enantioenriched chiral good yields with enantioselectivities.

Ruthenium- and rhodium-catalyzed direct oxidative cross-coupling reactions of acrylamides with alkenes were developed. These methods provide an efficient route for the synthesis (Z,E)-dienamides in excellent yields good stereoselectivity. The catalytic systems allowed olefination a wide range bearing different functional groups, such as CO2R, COMe, SO2Ph, aryl, CONHBn, CN, PO(OEt)2, well Weinreb amide.

Phosphine-catalyzed one-pot isomerization and [2 + 3]-cycloaddition of 3-butynoates with electron-deficient olefins affords highly functionalized cyclopentenes both good yields excellent selectivities up to 99%.