- SYNTHESIS AND CONFORMATIONAL ANALYSIS OF SOME OXISURAN METABOLITES AND THEIR O-METHYLDERIVATIVES
-
The synthesis is given of oxisuran (methylsulphinylmethyl-2-pyridyl ketone) and its metabolites and derivatives, whose structures are 2-Py-CO-CH2-SOxCH3 (X=0, 1, 2) and 2-Py-CHOR-CH2SOnCH3 (R=H, Me; n=0, 1, 2).From the results obtained in the reaction of oxisuran with different reducing agents, a new stereochemical pathway is suggested to explain the stereoselectivity observed in the reduction of β-ketosulphoxides with DIBAL.The conformational analysis of hydroxy and methoxyderivates is discussed in relation with that previously reported for 2-thioderivatives of phenylethanol and their O-methylderivates.The configurational assignment of diastereoisomeric sulphoxides is made on the basis of their different conformational behaviour, confirming the assigment deduced from the stereoselectivity observed in the reduction of oxisuran.
- Ruano, J. L. Garcia,Pedregal, C.,Rodriguez, J. H.
-
p. 4407 - 4416
(2007/10/02)
-
- REACTIVITIES OF ISOMERIC (1-DIMETHYLAMINOVINYL)PYRIDINES. REACTION WITH SULFENE
-
It is shown by means of quantum-chemical calculations (MINDO/3) and data from the 13C NMR and photoelectron (PE) spectra that a weak interaction between the enamine fragment and the heteroring, which deviates from its plane, exists in pyridyl enamines.The reaction of (1-dimethylaminovinyl)pyridines with sulfene leads to mixtures of 3-dimethylamino-3-pyridylthietane 1,1-dioxide (80percent) and the corresponding methylsulfonyl ketone, the yield of which decreases as the acceptor character of the aromatic ring increases (α-Py γ-Py β-Py Ph).The structures of the enamines and the products of their reaction with sulfene were proved by IR, UV, and PMR spectroscopy, mass spectrometry, and the results of elementary analysis.
- Koikov, L. N.,Terent'ev, P. B.,Gloriozov, I. P.,Torocheshnikov, V. N.,Baidin, V. N.,Bundel', Yu. G.
-
p. 518 - 524
(2007/10/02)
-