Tahir Daşkapan

Electrophilic Amination of Diarylzincs and Triarylzincates with Acetone -(2,4,6-Trimethylphenylsulfonyl) Oxime and with O-Methylhydroxylamine

Abstract Diarylzines and triarylzincates react efficiently with acetone O-(2,4,6-trimethylphenylsulfonyl) oxime and O-methylhydroxylamine in the presence of CuCN to give amines in good yields.

Can we aminate Grignard reagents under Barbier conditions

The reaction of aryl bromides with acetone O-(2,4,6-trimethylphenylsulfonyl)oxime and magnesium in THF at reflux temperature for 3 h provides a one-pot procedure for amination of aryl Grignard reagents under Barbier conditions.

Electrophilic amination of organozinc reagents with acetone O -(2,4,6-trimethylphenylsulfonyl)oxime and O -methylhydroxylamine

Reaction of diorganozincs and triorganozincates with acetone O-(2,4,6-trimethylphenylsulfonyl)oxime or O-methylhydroxylamine in the presence of CuCN provides a new one-flask method for electrophilic amination of organozinc reagents. Considering the lithium- or magnesium-to-zinc transmetallation, this method also extends the scope of electrophilic amination of organolithiums and Grignard reagents.

The Effectiveness of Copper(I) Compounds as Catalysts in the Coupling of Phenyllithium with Primary Alkyl Halides and Tosylates

Abstract Various uncomplexed and complexed Cu(I) salts, Li2CuCl4, Li2CuCl3, Ph2CuLi and PhCu, have been tested as catalysts in the coupling reactions of phenyllithium with 2-chloroethanol, ethyl bromide, 2-chloroethyl tosylate and ethyl tosylate. CuBr.Me2S,-CuCN, CuI.PBu3-n and Cul have been found to be the most effective and selective catalysts in diethyl ether, respectively, for these couplings. The catalytic activity in Cu(I) catalyzed coupling reactions of phenyllithium depends on the reaction conditions, on the nucleofugal group, and on the 2-heteroatom functionality of the substrate.

Accelerating Ligands for Osmium Tetraoxide Catalyzed Racemic Dihydroxylation of α-Pinene

Abstract Osmium tetraoxide catalyzed racemic cis-dihydroxylation of α-pinene usinf N-oxide as cooxidant and hexamethylenetetraamine as accelerating ligand in tert-butyl alcohol gives excellent yield of α-pinanediol.

Aryl C-N bond formation by electrophilic amination of diarylcadmium reagents with O-substituted ketoximes

ABSTRACT Diorganocadmium reagents cannot react with ketoxime at room temperature. CuCN catalysis allows diarylcadmium reagents to react with ketoxime and to give corresponding arylamines in good to high yields at room temperature. According to the electronic effects of the substituent attached to the aromatic ring, functionalized diarylcadmium reagents show meta-para selectivity in their amination reactions. Also compared to diarylzinc reagents, diarylcadmium reagents react with O-substituted ketoxime under milder reaction conditions and they form corresponding arylamines in higher yields. CuCN cannot help dialkyl-, dicycloalky-, and dibenzylcadmium reagents to react with ketoxime. Our Aryl C-N bond formation method does not include cadmium excretion into the environment. GRAPHICAL ABSTRACT

High yielding electrophilic amination method for arylcopper reagents

ABSTRACT The facilitative effect of some P-, N-, S-, and O-donor ligands in the reaction of arylcoppers with acetone O-(mesitylenesulfonyl)oxime was examined to develop a synthesis method for functionalized primary aryl amines under mild reaction conditions. Our research showed that electrophilic amination of monoaryl coppers with ketoximes can be facilitated using appropriate ligand to supply significant increase in the yield. Also, we have seen that this ligand-facilitated method is applicable in terms of arylcopper and ketoxime type and allows synthesis of primary aryl amines in good to high yields easily at room temperature in very short reaction time. GRAPHICAL ABSTRACT