The N-heterocyclic carbene (NHC)-catalysed redox amidation reaction is poorly developed and usually requires catalytic co-additives for electron-rich amine nucleophiles. We report a masking strategy (using CO2) that couples release of the free amine nucleophile to catalytic turnover, and in doing so, enables direct catalytic redox amidation of electron-rich amines.

A catalytic enantioselective syn-1,4-bromolactonization of conjugated (Z)-enynes was reported. Diastereomeric ratios >20:1 and up to 99% enantiomeric excesses were observed. Di-, tri-, and tetra-substituted bromoallenes were prepared together with lactone heterocycles efficiently and stereoselectively. Preliminary investigations suggest that the chiral catalyst may serve as a bifunctional reage...

An efficient synthetic method of 1,3-bis(arylethynyl)isobenzofurans is developed. Nucleophilic addition of alkynyllithium to benzocyclobutenone and subsequent oxidative ring cleavage of the four-membered ring gave a keto-aldehyde, which, in turn, accepted the second nucleophile to produce isobenzofurans after acid treatment.

A new strategy has been developed for the benzylation of nitriles directly from benzyl alcohols. In this process benzyl alcohols undergo retro-Claisen activation with cyanoacetic esters to generate an active electrophile and a carbanionic nucleophile. In the presence of Pd(0) these intermediates undergo catalytic coupling to generate a new C-C bond, resulting in the formation of phenyl propioni...

The minute amount of hydrogen sulfate groups introduced into the graphene oxide (GO) obtained by Hummers oxidation of graphite renders this material as a highly efficient, recyclable acid catalyst for the ring opening of epoxides with methanol and other primary alcohols as nucleophile and solvent.

Kinetic resolution of racemic planar-chiral metallocenes was performed through the conjugate addition of a nucleophile to the enal part of substrates. While no enantiomeric discrimination was found with low-molecular-weight organocatalysts, a properly designed resin-supported peptide catalyzed the reaction in a highly selective manner.

The copper-catalyzed ketenimine formation reaction of 1-(o-acetamidophenyl)propargyl alcohols with various sulfonyl azides is found to undergo a concomitant intramolecular nucleophile attack to generate 1,2-dihydro-2-iminoquinolines after aromatization (via elimination of acetyl and hydroxy groups) and tautomerization. The reaction produces 4-substituted and 3,4-unsubstituted title compounds in...

Enantiomerically enriched hydroxy-substituted beta-amino esters have been synthesized through CAL-B-catalyzed enantioselective hydrolysis in organic media. Moderate to good enantiomeric excess values (ee > or = 52%) were obtained when the CAL-B-catalyzed reactions were performed in t-BuOMe, at 60 degrees C with 0.5 equiv. of added H(2)O as nucleophile.

Control of boronic acid speciation is presented as a strategy to achieve nucleophile chemoselectivity in the Suzuki-Miyaura reaction. Combined with simultaneous control of oxidative addition and transmetalation, this enables chemoselective formation of two C-C bonds in a single operation, providing a method for the rapid preparation of highly functionalized carbogenic frameworks.

The palladium-catalyzed reaction of 2,3,3-trifluoroallyl esters with several types of amines afforded trifluoromethylenamines, which were formed by the addition of a nitrogen nucleophile at the C-2 position and the intramolecular construction of the trifluoromethyl group via the fluorine atom shift from the C-2 to the C-3 position.