Yu. D. Grudtsyn

Regioselectivity in the reactions of the acetonate ion with electron-deficient arenes

The reactions of the acetonate ion with 1,3-dinitro-5-X-, 1,3-X2-5-nitro- (X = NO2, CN, COOCH3, CONH2, COO–, and H), and 1,3,5-tricyanobenzenes were studied by 1H NMR and electronic absorption spectroscopy and by quantum-chemical methods. The kinetic factor is decisive for the initial attack of the carbanion on the C(2) atom of unsymmetrical arenes. However, σ-adducts in which a nucleophile is added to the C(4) atom are more stable thermodynamically. In the case of 1,3-X2-5-nitrobenzenes (X = CN, COOCH3, or CONH2), the σ-adducts with the acetonate group in para-position to the X group unexpectedly proved to be very stable. The structures of the σ-adducts based on trinitro- and 1,3-dinitro-5-cyanobenzenes were determined by X-ray diffraction analysis. Quantum-chemical calculations (the AM1 and PM3 semiempirical methods and the density functional method) were used to interpret the reaction regioselectivity and the molecular and electronic structures of the σ-adducts.

3-Azabicyclo[3.3.1]nonane Derivatives: III. Synthesis of 3-Substituted 9-Acetonyl-1,5-dinitro-3-azabicyclo[3.3.1]-non-6-en-8-ones by Mannich Condensation of the Janovsky σ-Adduct of 2,4-Dinitrophenol with Acetonide Ion

A number of 9-acetonyl-1,5-dinitro-3-azabicyclo[3.3.1]non-6-en-8-one derivatives were synthesized by Mannich condensation of 3-acetonyl-2,4-bis(aci-nitro)cyclohex-5-en-1-one disodium salt with formaldehyde and primary amines.

3-Azabicyclo[3.3.1]nonane Derivatives: V. Synthesis of 7-Polyfluoroalkoxy-1,5-dinitro-3-azabicyclo[3.3.1]non-6-enes

A number of 7-polyfluoroalkoxy-1,5-dinitro-3-azabicyclo[3.3.1]non-6-enes were synthesized by reduction of 3,5-dinitrophenyl polyfluoroalkyl ethers with sodium tetrahydridoborate, followed by the Mannich reaction with formaldehyde and primary amines.

3-Azabicyclo(3.3.1)nonane Derivatives: IV. * Synthesis of Amino Acids with 3-Azabicyclo(3.3.1)nonane Fragment **

A series of 1.5-dinitro-3-azabicyclo[3.3.1]non-6-enes was prepared by reduction of 1-R-2,4- and 1-R-3,5-dinitrobenzenes with potassium borohydride followed by Mannich reaction with formaldehyde and amino acids. The molecular structure of (6-bromo-1,5-dinitro-3-azabicyclo[3.3.1]non-6-en-3-yl)acetic acid was studied by X-ray diffraction analysis. The mechanism of decomposition under electron impact was determined for (7-methoxy-1,5-dinitro-3-azabicyclo[3.3.1]non-6-en-3-yl)acetic acid.

Hydroformylation of 1-octene in the presence of cobalt alkylidynecarbonyl clusters

The hydroformylation of 1-octene in the presence of Co3(CO)9(μ-CR) (R=H, Me, Ph, CO2Me, CO2Et, CO2Pri, CO2But, Cl, Br, OMe) alkylidynecarbonyl clusters, as well as triphenylphosphine derivatives of these complexes and heteronuclear Co2Ni compounds have been studied. The nature of the catalytically active species in hydroformylation, as well as the processes of their formation and transformation during the reaction, have been established by means of IR spectroscopy. The effects of the reaction conditions, the nature of the substituent at the apical carbon atom, the electron donating phosphine substituent, and the substituent in the metal cluster framework have been discussed.