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The reactions of 1-benzoyl-2,4-diphenyl-2,3-dihydro-1H-1,5-benzodiazepine with methyl 1-bromocycloalkanecarboxylates and zinc, followed by hydrolysis of the reaction mixtures, resulted in the formation of spiro-δ-lactams bearing a 2-(N-benzoylamino)phenyl substituent at the nitrogen atom. The product structures were confirmed by X-ray structural analysis, and a mechanism was proposed for the product formation.

A study of ion-molecular reactions of fluoro-substituted phenyl cations with benzopyridine derivatives demonstrated the following: (a) at present only the nuclear-chemical method enables the reaction of a direct phenylation of the nitrogen atom in benzopyridine derivatives, which makes it possible to obtain previously unknown quaternized structures, and (b) generation of nucleogenic phenyl cations with various substituents leads to a simultaneous introduction of the required substituents into the aromatic ring at the nitrogen heteroatom. Quantum-chemical calculations additionally confirmed the assumption about the pathways of the ion-molecular reactions with nucleogenic phenyl cations.

Reformatsky reaction of methyl 1-bromocyclopentane-1-carboxylic acid with 3-aryl-2-cyanoprop-2-enamides and their N-methyl derivatives afforded 10-aryl-6,8-dioxo-7-azaspiro[4.5]decane-9-carbonitriles and 10-aryl-7-methyl-6,8-dioxo-7-azaspiro[4.5]decane-9-carbonitriles, respectively.

Methyl 1-bromocyclohexanecarboxylate reacts with zinc and amides or methylamides of 3-aryl-2-cyanopropenoic acids to give 5-aryl-1,3-dioxo-2-azaspiro[5.5]undecane-4-carbonitriles or 5-aryl-2-methyl-1,3-dioxo-2-azaspiro[5.5]undecane-4-carbonitriles.

Methyl 1-bromocyclopentane-, 1-bromocyclohexane-, and 1-bromocycloheptanecarboxylates react with zinc and 2,6-bis(arylmethylene)cyclohexanones to afford 4-aryl-8-(arylmethylene)-5,6,7,8-tetrahydrospiro[chromene-3,1′-cyclopentan]-2(4H)-ones, 4-aryl-8-(arylmethylene)-5,6,7,8-tetrahydrospiro[chromene-3,1′-cyclohexan]-2(4H)-ones, and 4-aryl-8-(arylmethylene)-5,6,7,8-tetrahydrospiro[chromene-3,1′-cycloheptan]-2(4H)-ones, respectively.

Reaction of methyl 1-bromocyclobutanecarboxylate with zinc and 1-aryl-2-(arylimino)ethanones leads to 4,6a-diaryl-3,3:6,6-dipropano- tetrahydro-2H-furo[3,2-b]pyrrole-2,5(3H)-diones. Structure of one of these compounds is confirmed by X-ray analysis.

The Reformatsky reagents derived from methyl 1-bromocyclohexane-or 1-bromocyclopentanecarboxylate and zinc add to benzoin to afford the corresponding 4-hydroxy-3,4-diphenyl-2-oxaspiro[4.5]decan-1-one and 4-hydroxy-3,4-diphenyl-2-oxaspiro[4.4]nonan-1-one.

Dimethyl 2-(1-bromocyclohexylcarbonyl)-, 2-(1-bromocyclopentylcarbonyl)-, and 2-(1-bromocyclobutylcarbonyl)-2-methylmalonates reacted with zinc and aromatic aldehydes to give the corresponding methyl 1-aryl-4-methyl-3,5-dioxo-2-oxaspiro[5.5]undecane-4-, 6-aryl-9-methyl-8,10-dioxo-7-oxaspiro[4.5]-decane-9-, and 5-aryl-8-methyl-7,9-dioxo-6-oxaspiro[3.5]nonane-8-carboxylates.

Zinc enolates obtained from substituted 1-aryl-2,2-dibromoalkanones and zinc react with alkyl 3-oxo-1,3-dihydrobenzo[c]oxepine-4-carboxylate to give the alkyl 1-alkyl-1-aroyl-2-oxo-4,8b-dihydro-1H-3-oxabenzo[a]cyclopropa[c]cycloheptene-1a-carboxylate.

Zinc enolates formed from 1-aryl-2-bromo-2-phenylethanones and zinc react with dimethyl 2-(1-arylmethylene)malonates to afford dimethyl 2-(1,3-diaryl-3-oxo-2-phenylpropyl)malonates. The latter react with cyclohexylamine, piperidine, or morpholine to give the corresponding monosubstituted amides. The zinc enolate derived from 2-bromoindanone and zinc reacts with dimethyl 2-(4-bromobenzylidene)malonate, yielding dimethyl 2-[(4-bromophenyl)(1-oxoindan-2-yl)methyl]malonate. The final products largely form as a single diastereomer.

The Reformatskii reagents formed from alkyl esters of α-bromoacetic, α-bromopropanoic, and α-bromoisobutyric acids and zinc react with N-arylamides of 2-oxochromene-3-carboxylic acid, yielding 3-R1-1-R2-1-R3-4a,10b-dihydro-1H-chromeno[3,4-c]pyridine-2,4,5-triones.

Zinc enolates formed from 1-aryl-2-bromoalkanones react with methyl esters of substituted 2-oxochromene-3-carboxylic acids to give methyl esters of 6-bromo- or 6,8-dibromo-4-(2-aryl-2-oxo-1-R- ethyl)-2-oxochromane-3-carboxylic acids as mixtures of two diastereomers.

Reaction of methyl 1-bromocyclobutanecarboxylate with zinc and 1-aryl-2-(arylimino)ethanones leads to 4,6a-diaryl-3,3:6,6-dipropano- tetrahydro-2H-furo[3,2-b]pyrrole-2,5(3H)-diones. Structure of one of these compounds is confirmed by X-ray analysis.

Treatment of methyl 1-(2-bromo-4-methoxy-1,4-dioxobutyl)cyclohexanecarboxylate with zinc followed by aromatic aldehydes affords methyl 1-(2-aryl-5-oxotetrahydrofuran-3-carbonyl)cyclohexanecarboxylates.

Reformatsky reagent prepared from methyl 1-bromocyclopentanecarboxylate and zinc reacted with 2-oxochromen-and 6-bromo-2-oxochromen-3-carboxylic acids N-arylamides yielding 3-aryl-1,1-tetramethylene-and 3-aryl-9-bromo-1,1-tetramethylene-2,3,4,4a,5,10b-hexahydro-1H-chromeno[3,4-c]pyridine-2,4,5-triones as single diastereomers.

Methyl 4-bromo-3-oxo-2,2,4-trimethylpentanoate reacts with zinc and arylglyoxals yielding 6-aroyl-3,3,5,5-tetramethyl-2,3,5,6-tetrahydropyran-2,4-diones. The latter with phenylhydrazine afford 6-(1-aryl-2-phenylhydrazonomethyl)-3,3,5,5-tetramethyl-2,3,5,6-tetrahydropyran-2,4-diones.

Treatment of methyl 1-(2-bromo-4-methoxy-1,4-dioxobutyl)cyclohexanecarboxylate with zinc followed by aromatic aldehydes affords methyl 1-(2-aryl-5-oxotetrahydrofuran-3-carbonyl)cyclohexanecarboxylates.

Methyl 4-bromo-3-oxo-2,2,4-trimethylpentanoate reacts with zinc and arylglyoxals yielding 6-aroyl-3,3,5,5-tetramethyl-2,3,5,6-tetrahydropyran-2,4-diones. The latter with phenylhydrazine afford 6-(1-aryl-2-phenylhydrazonomethyl)-3,3,5,5-tetramethyl-2,3,5,6-tetrahydropyran-2,4-diones.

Reformatsky reagent prepared from methyl 1-bromocyclopentanecarboxylate and zinc reacted with 2-oxochromen-and 6-bromo-2-oxochromen-3-carboxylic acids N-arylamides yielding 3-aryl-1,1-tetramethylene-and 3-aryl-9-bromo-1,1-tetramethylene-2,3,4,4a,5,10b-hexahydro-1H-chromeno[3,4-c]pyridine-2,4,5-triones as single diastereomers.

Interaction of methyl 1-bromocyclobutanecarboxylate with zinc and 1,2-diphenyl-1,2-ethanedione affords the title compound, whose structure was confirmed by X-ray analysis.