V. V. Zorin

Stereoselective synthesis of allylamines by iron-catalyzed cross-coupling of 3-chloroprop-2-en-1-amines with grignard reagents. Synthesis of naftifine

A general procedure for the synthesis of trans- and cis-allylamines has been developed on the basis of iron-catalyzed cross-coupling of Grignard reagents with stereochemically pure 3-chloroprop-2-en-1-amines prepared by allylation of amines with commercially available 1,3-dichloropropene isomers.

A new approach to the synthesis of ethyl (4E)-alkenoates

A new approach to the preparation of ethyl (4E)-alkenoates was developed on the basis of Fe-catalyzed cross-coupling of ethyl (4E)-5-chloropent-4-enoate with the Grignard reagents. The starting ethyl (4E)-5-chloropent-4-enoate was obtained by alkylation of malonic ester of (E)-1,3-dichloropropene followed by decarbethoxylation.

Fe-catalyzed synthesis of (4E)-tridec-4-en-1-yl acetate, sex pheromone of tomato pinworm (Keiferia lycopersicella)

Starting with industrially available 1,3-dichloropropene a stereoselective process was developed for the preparation of (4E)-tridec-4-en-1-yl acetate, sex pheromone of tomato pinworm (Keiferia lycopersicella) using in the key stage the Fe-catalyzed cross-coupling of ethyl (4E)-5-chloropent-4-enoate with octylmagnesium bromide.

Iron-catalyzed synthesis of cinnarizine

Cinnarizine was synthesized in a high yield by iron-catalyzed cross-coupling of phenylmagnesium chloride with 1-[(2E)-3-chloroprop-2-en-1-yl]-4-(diphenylmethyl)piperazine prepared by allylation of 1-(diphenylmethyl) piperazine with (E)-1,3-dichloropropene.

Synthesis of (4E,6Z)-Hexadeca-4,6-dien-1-ol and Its Acetate – Components of the Sex Pheromone of Stathmopoda masinissa

(4E,6Z)-Hexadeca-4,6-dien-1-ol and its acetate, components of the sex pheromone of the moth Stathmopoda masinissa, were synthesized stereospecifically via Pd-catalyzed cross-coupling of ethyl (4E)-5-chloropent-4-enoate, which was obtained from industrially available (E)-1,3-dichloropropene, and undec-1-yne.

Fe-Catalyzed Synthesis of (13Z)-Eicos-13-en-10-one, the Main Sex Pheromone Component of Carposina niponensis

(13Z)-Eicos-13-en-10-one, the main sex pheromone component of Carposina niponensis, was synthesized stereoselectively via Fe-catalyzed cross-coupling of ethyl (4Z)-5-chloropent-4-enoate with hexylmagnesiumbromide to give ethyl (4Z)-undec-4-enoate and repeated Fe-catalyzed cross-coupling of its acid chloride with nonylmagnesiumbromide.

Fe-catalyzed synthesis of flunarizine and its (Z)-isomer

Flunarizine {Sibelium, 1-[bis(4-fluorophenyl)methyl]4-[(2E)-3-phenylprop-2-en-1-yl]piperazine} is a wellknown drug belonging to calcium channel blockers. It exhibits vasodilating effect, improves cerebral blood circulation, and shows antihistamine activity. Flunarizine is used to treat migraines, dizziness, vestibular disorders, and epilepsy [1–4]. Industrial production of flunarizine is based on condensation of N-cynnamylpiperazine with bis(4-fluorophenyl)chloromethane or of cynnamyl chloride with 1-[bis(4-fluorophenyl)methyl]piperazine [5, 6]. Flunarizine can be obtained by regioselective metal-catalyzed amination of cinnamyl alcohol with 1-[bis(4-fluorophenyl)methyl]piperazine using Pt(cod)2Cl2–DPEPhos [7] and Pd(OAc)2–1,10phenanthroline catalysts [8]. (E)and (Z)-isomers of 1[bis(4-fluorophenyl)methyl]-4-(3-phenylprop-2-en-1yl)piperazine (E : Z = 1 : 7.4) have been also prepared via Wittig reaction involving {4-[bis(4-fluorophenyl)methyl]piperazin-1-yl}acetaldehyde and benzyltriphenylphosphonium chloride, followed by isomers separation by column chromatography [9].

Pd-Cu-catalyzed synthesis of N-(2E,4)- and N-(2Z,4)-enyne cyclic amines

By Pd-Cu-catalyzed coupling of (2E)- and (2Z)-3-chloroprop-2-en-1-ylamines and alkynes a stereoselective method of the synthesis was developed for a series of (2E,4)- and (2Z,4)-enyne cyclic amines.

Synthesis of ethyl (4E)-tridec-4-ene-6-ynoate

Various cross-coupling reactions based on vinyl halides, which proceed with the retention of the double bond configuration (Negishi, Sonogashira, Suzuki, Stille, Heck reactions), are widely used to create the carbon-carbon bonds in the synthesis of the practically useful unsaturated compounds [1–5]. Previously, we have synthesized the stereochemically pure chlorovinyl-derived malonic esters, which are of great interest for the synthesis of valuable intermediates used to obtain the biologically active substances. So, in order to obtain ethyl (4E)-tridec-4-ene-6-ynoate III, which is a precursor of some low-molecular bioregulators including insect pheromones with the structure of conjugated diene and enyne acids, alcohols and acetates [6, 7], we performed the reaction of (E)1,3-dichloropropene with malonic ester under the phase transfer catalysis followed by the Krapcho decarboxylation [8] to produce the stereochemically pure ethyl (4E)-5-chloropent-4-enoate [9].

Fe-catalyzed synthesis of (4 Z )-alkenoates

A new approach to stereoselective synthesis of (4Z)-alkenoates has been developed based on Fecatalyzed cross-coupling of ethyl (4Z)-5-chloropent-4-enoate with the Grignard reagents.