Enamines as Surrogates of Alkyl Carbanions for the Direct Conversion of Secondary Amides to α-Branched Ketones
A direct transformation of secondary amides into α-branched ketones with enamines as soft alkylation reagents was developed. In this reaction, enamines serve as surrogates of alkyl carbanions, rather than the conventional enolates equivalents in the Stork's reactions, which allowed for the easy introduction of alkyl groups with electrophilic functional groups. In the presence of 4 ? molecular sieves, the method can be extended to the one-pot coupling of secondary amides with aldehydes to yield ketones. (Figure presented.).
Synthesis of coordinatively unsaturated iridium complexes having functional 8-quinolinolato ligands: New catalysts for dehydrogenative oxidation of alcohols in aqueous media
New iridium complexes having functional 8-quinolinolato ligands have been synthesized. By single-crystal X-ray analysis, it was revealed that these new complexes had coordinatively unsaturated structure (five-coordinate trivalent iridium: 16e- complex). Furthermore, one of the new complexes exhibited high catalytic activity for the dehydrogenative oxidation of various aromatic and aliphatic secondary alcohols in aqueous media to give the corresponding ketones in good to excellent yields.
Toyomura, Kazuki,Fujita, Ken-Ichi
supporting information
p. 808 - 810
(2017/06/13)
Efficient synthesis of alkyl aryl ketones & ketals via palladium-catalyzed regioselective arylation of vinyl ethers
The combination of Pd(OAc)2 with 1,3-bis(diphenylphosphino) propane (dppp) in ethylene glycol constitutes a high-performance catalytic system for highly regioselective arylation of a range of electron-rich vinyl ethers by aryl bromides to provide, upon hydrolysis, alkyl aryl ketones and cyclic ketals in good yields with up to 3.75 × 105 TON and 15625 h-1 TOF.