Asymmetric michael addition of aromatic thiols to 2-cyclohexenone and maleic acid esters via formation of crystalline cyclodextrin complexes

The asymmetric Michael addition of aromatic thiols to 2-cyclohexenone and maleic acid esters has been carried out by utilizing their crystalline cyclodextrin complexes suspended in water. The best chiral induction, 30% enantiomeric excess (ee), was achieved in combinations of 2-cyclohexenone and octyl maleate with the crystalline -cyclodextrin complex of benzenethiol (method A) to afford (S)-3-phenylthiocyclohexanone and (S)-octyl-2-phenylthiosuccinate, respectively, whereas the reaction of benzenethiol with 2-cyclohexenone included in -cyclodextrin (method B) inversely induced the chiral recognition to give the (R)-adduct with 4–9% ee.     

π‐Facial Selectivity in the Formation of Tricarbonylchromium(0) Complexes of Estra‐1, 3, 5(10), 6‐tetraenes

The preparation of two η⁶‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation.     

Convenient preparative method for synthesis of methyl (Z)-3-aryl-2-(carbobenzoxyamino)acrylates by Wittig—Horner reaction with the use of Et3N as a base

The Wittig—Horner reaction of CbzNHCH(CO₂Me)P(O)(OMe)₂ (1) with ArCHO (2) in the presence of Et₃N as a base affords methyl (Z)-3-aryl-2-(carbobenzoxyamino)acrylates (3) with high degrees of diastereoselectivity (Z)/(E) > 101. One recrystallization of the crude product is sufficient to obtain isomerically and chemically pure (Z)-3.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2218-2220, November, 1995.The authors are grateful to the Dupont company (USA) for financing this study     

Formation of 2,2-difluoro-3-hydroxymethylbenzo-1,4-oxathianes from 2-(α-trifluoromethylvinylthio)phenols)

It is shown that 2,2-difluoro-3-hydroxymethylbenzo-1,4-oxathianes are formed together with 3-trifluoromethylbenzo-1,4-oxathianes whenortho-(-trifluoromethyl--chloroethylthio)phenols are boiled with excess aqueous alkali. The mechanism of the reaction is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1457–1459, August, 1994.     

Vibrational spectra and structure of “staircase” carbonyl π-complexes of transition metals

FTIR spectra have been studied for staircase cyclopentadienyl complexes containing two or three metal carbonyl fragments bound by the metal-carbon bond Cp(CO)₂Fe-CpmMn(CO)₃ (1), Cp(CO)₂Fe-CpmFe(CO)₂CH₂Ph (2), Cp(CO)₂Fe-Cpm(CO)₂Fe-CpmMn(CO)₃ (3), Cp(CO)₂Mo-Cpm(CO)₂Fe-CpmMn(CO)₃ (4), Cp(CO)₃W-Cpm(CO)₂Fe-CpmMn(CO)₃ (5), Cp(CO)₂Fe-Cpm(CO)₂Fe-BmCr(CO)₃ (6), Cr(CO)₃Bm-CpmFe(CO)₂CH₂Ph (7), where Cp = ₅-C₅H₅, Cpm = ¹⁵-C₅H₄, Bm = ¹⁶-C₆H₅. Temperature-dependent FTIR spectra were measured inn-pentane solutions over a wide temperature range and in the low-temperature solid matrices of argon and nitrogen. Rotamers, formed due to rotation about the metal-carbon -bond, were found in solutions and matrices. A molecular mechanics calculation of1 proved the possibility of such rotation.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1952–1956, November, 1994.The authors are grateful to the Russian Foundation for Basic Research (project code No 93-03-18592) and to the International Science Foundation (project code No MEQ000).     

Physicochemical properties of π-π complexes of zinctetraphenylporphyrin with aromatic molecules

Features of the solvation of zinctetraphenylporphyrin (ZnTPP) in benzene, toluene,ortho-, meta-, andpara-xylenes were studied by a thermogravimetric method. The temperature ranges of the stability and the compositions of the corresponding specific - complexes were determined from the results of the thermogravimetric investigation of the crystallosolvates of the metalloporphyrin with the solvent molecules, and the energy characteristics of the intermolecular metalloporphyrin—solvent interactions were calculated.Institute of the Chemistry of Nonaqueous Solutions, Russian Academy of Sciences, 153018 Ivanovo. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1545–1548, July, 1992.     

Kinetics and mechanism of reaction of cis-α,β-dinitrostilbene with morpholine

Reaction of cis-,-dinitrostilbene (substrate) with morpholine (reagent) in n-hexane leads to cis--nitro--morpholinostilbene (end product). The process is of first order with respect to the substrate and second order with respect to the reagent. Possible reaction mechanisms are analyzed, and it is established that the following are most probable on the basis of kinetic patterns and stereochemistry: development of a charge transfer complex having a hydrogen bond between the substrate nitro group and reagent amino group; reaction of the complex with a second reagent molecule and formation of a carbanion (this stage determines the overall reaction rate); and detachment of a nitrite ion from the nitrocarbanion and its protonation to form the end product.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. A. N. Nesmeyanov Institute of Heteroorganic Compound, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 78–83, January, 1992.     

Reaction paths of some open-shell reactive intermediates

The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (^1,3CH₂), the additions of carbenes (^1,3CH₂ and^1,3CF₂) as well as amino radicals (²NH₂ and²NF₂) toward ethylene, and the hydrogen abstractions by methylenes (^1,3CH₂), nitrene (³NH), and hydroxyl radical (²OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions.     

A molecular modelling study of the interaction of noradrenaline with theβ 2-adrenergic receptor

Summary A model of the ₂-adrenergic receptor binding site is built from the primary structure of the receptor, experimental evidence for key binding residues and analogy with a homologous protein of partially determined structure. It is suggested that residues Trp-109, Thr-110 and Asp-113 are involved in ligand binding. Noradrenaline is successfully docked into this model, and the results of an INDO molecular orbital calculation on the complex indicate that a charge transfer interaction between Trp-109 and noradrenaline is possible.     

Electrochemical synthesis of π-indenyl-π-(3)-1,2-dicarbollyliron(III)

Co-electrolysis of potassium 1,2-dicarbadodecahydroundecaborate and indene in 0.1N sodium bromide solution in dimethylsulfoxide using iron electrodes afforded -indenyl--(3)-1,2-dicarbollyliron(III).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 764–765, April, 1993.