Giuseppe Marchese

Iron catalyzed cross-coupling reactions of acyl chlorides with Grignard reagents. A mild, general, and convenient synthesis of aliphatic and aromatic ketones

Abstract Acyl chlorides couple with Grignard reagents at room temperature in the presence of catalytic amounts of tris(acetylacetonate)iron(III), Fe(acac) 3 . The reaction is general with respect to both reactants and provides a very mild and convenient method for the synthesis of aliphatic and aromatic ketones.

A highly efficient synthetic route to ketones through sequential coupling reactions of Grignard reagents with S-phenyl carbonochloridothioate in the presence of nickel or iron catalysts

Abstract The sequential coupling reactions of Grignard reagents with S phenyl carbonochloridothioate in the presence of nickel(II) or iron(III) catalysts provides a very mild and straightforward route to symmetrical and unsymmetrical aliphatic and aromatic ketones.

A direct access to α-diones from oxalyl chloride

Abstract Cross-coupling reactions of oxalyl chloride with organocopper reagents, derived from Grignard reagents, cuprous bromide, and lithium bromide, provide a simple and straightforward method for the synthesis of symmetrical α-diones in very good yields.

Functionalized ketones by iron mediated reaction of grignard reagents with acyl chlorides

Abstract The iron(III)-catalyzed cross-coupling reaction between Grignard reagents and acyl chlorides was found to be widely applicable to the synthesis of various functionalized ketones in good yields under mild conditions; the series of examples includes the synthesis of chiral methyl ketones and symmetric diketones.

ONE-STEP SYNTHESIS OF DIALKYNYL-1,2-DIONES AND THEIR CONVERSION TO FUSED PYRAZINES BEARING ENEDIYNE UNITS

Abstract A convenient procedure for the preparation of symmetrically end-protected dialkynyl-1,2-diones 3 from lithium acetylides and oxalyl chloride in the presence of CuBr and LiBr is described. The condensation of 3 with various aromatic and heteroaromatic 1,2-diamines leads to pyrazine-based α-dialkynylated heterocycles. The enediyne substructure of diethynylquinoxaline can be thermally rearranged in a Bergman cyclization reaction.

Stereospecific synthesis of (1E,3Z)- and (1E,3E)-1-trimethylsilyl-1,3- dienes by means of sequential cross-coupling reactions

Abstract A new synthesis of stereodefined 1-trimethyl-1,3-dienes is described. The method is based on two sequential coupling reactions between Grignard and the readily available (Z)- or (E)-1-bromo-2-phenyl-thioethene, in the presence of transition metal catalysts.

A general and straightforward approach to α,ω-ketoesters

Abstract Chemoselective cross-coupling reactions of monoesters of dicarboxylic acid chlorides with organocopper reagents derived from Grignard reagents, cuprous bromide, and lithium bromide, provide a simple and straightforward method for synthesizing a variety of ketoesters.

One-step synthesis of ketones from car☐ylic acids and grignard reagents in the presence of a nickel(II)-phosphine catalyst.

Abstract A one-step synthesis of diaryl and alkyl-aryl ketones by the reaction of car☐ylic acid with Grignard reagents in the presence of NiCl2(Ph2PCH2CH2PPh2) as catalyst is described. In the nickel-catalyzed Grignard reaction the formation of alcohols is nearly completely suppressed.

A new ready route to 1,4-ketoaldehydes and 1,4-diketones with application to the synthesis of z-jasmone and dihydrojasmone

Abstract A new three-step synthesis in good overall yield of 1,4-ketoaldehydes and 1,4-diketones is described. The method involves two sequential coupling reactions of Grignard reagents with S-phenyl carbonochloridothioate in the presence of nickel(II) or iron(III) complexes as catalysts. Application of this reaction to the synthesis of Z-jasmone and dihydrojasmone is also described.

An easy route to insect pheromones with a E-Z or Z-E conjugated diene structure

Abstract Insect pheromones having a conjugated diene system of E-Z or Z-E configuration can be prepared with high stereoselectivity, by means of addition reactions of Z -dialkenyl cuprates to phenylthioacetylene. The alkadienyl sulphides intermediates are then subjected to a cross-coupling reaction with Grignard reagents, in the presence of a Ni(II) complex as a catalyst, leading to the desired pheromones.