An EtPPh(2)- or PPh(3)-catalyzed tandem three-component reaction of aldehyde, alkyl vinyl ketone, and amide is developed. Its further application in one-pot syntheses of highly functional alkenes starting from aldehydes, alkyl vinyl ketones, and amides is realized. A wide variety of highly functional α,β-unsaturated ketones can be furnished in 68-99% yields with high stereoselectivity (E/Z up t...

Palladium-catalyzed asymmetric allylic alkylation of ketones, via enamines generated in situ as nucleophiles, were carried out smoothly with chiral metallocene-based P,N-ligands. Under the same conditions, however, reactions of aldehydes could hardly be observed. Subsequently, this obstacle was resolved by using chiral metallocene-based P,P-ligands. Both ketones and aldehydes afforded excellent...

One of the most powerful synthetic transformations with the ability to stereospecifically create new carbon-carbon bonds by simple orbital reorganization are electrocyclic reactions. One of the most recognized electrocyclic reactions is known as Nazarov cyclization. This reaction involves the conversion of divinyl ketones to cyclopentenones by activation with a Brønsted or Lewis acid. It was or...

[reaction: see text] Very practical synthesis of ephedrine analogues in high yields and enantiopurity was realized by a highly diastereoselective Meerwein-Ponndorf-Verley (MPV) reduction of protected alpha-amino aromatic ketones using catalytic aluminum isopropoxide. The high anti selectivity resulted from the chelation of the nitrogen anion to the aluminum. In contrast, high syn selectivity wa...

A simple and versatile method for the synthesis of 1,5-benzodiazepines is via condensation of o-phenylenediamines (OPDA) and ketones in the presence of catalytic amount of H-MCM-22 using acetonitrile as solvent at room temperature. In all the cases, the reactions are highly selective and are completed within 1-3 h. The method is applicable to both cyclic and acyclic ketones without significant ...

The first enantioselective copper-catalyzed decarboxylative propargylic alkylation has been developed. Treatment of propargyl β-ketoesters with a catalyst, prepared in situ from [Cu(CH3 CN)4 BF4 ] and a newly developed chiral tridentate ketimine P,N,N-ligand under mild reaction conditions, generates β-ethynyl ketones in good yields and with high enantioselectivities without requiring the pregen...

Direct C-F functionalization of benzylic sp(3) C-H bonds is a synthetic challenge that has yet to be propitiously overcome. A mild, one-pot synthesis of monofluorinated benzylic substrates is reported with commercially available iron(II) acetylacetonate and Selectfluor in good to excellent yields and selectivity. A convenient route to β-fluorinated products of 3-aryl ketones is also highlighted...

A new method for the electrophilic α-alkynylation of ketones was developed using hypervalent iodine under mild and metal-free conditions. Carbonyl compounds containing an α-acetylene group were obtained in good to excellent yields for several ketones using 1-[(trimethylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one (TMS-EBX) as an alkynylation agent in the presence of t-BuOK and TBAF in THF as solven...

An environmentally benign, clean and general protocol was developed for the synthesis of aryl and heteroaryl trans-chalcones. This method involved solvent-free reaction conditions under microwave irradiation in the presence of a clay-based catalyst, and afforded the target compounds in good yields and short reaction times. Furthermore, the same conditions allowed the synthesis of symmetrical, d...

The first catalytic enantioselective conjugate alkynylation of α,β-unsaturated 1,1,1-trifluoromethyl ketones has been carried out. Terminal alkynes and 1,3-diynes were treated with trifluoromethyl ketones in the presence of a low catalytic load of a Cu(I) -MeOBIPHEP complex (2.5 mol %) and triethylamine (10 mol %) to give the corresponding trifluoromethyl ketones bearing a propargylic stereogen...