Synthesis of Side-Chain Locked Analogs of 1α,25-Dihydroxyvitamin D3 Bearing a C17 Methyl Group

2018 ◽  
Vol 20 (9) ◽  
pp. 2641-2644 ◽  
Author(s):  
Rita Sigüeiro ◽  
Miguel A. Maestro ◽  
Antonio Mouriño
2021 ◽  
Vol 67 (1) ◽  
Author(s):  
Shirong Sun ◽  
Tomoya Yokoyama

AbstractMonomeric C6-C2-type lignin model compounds with a p-hydroxyphenyl (H), guaiacyl (G), syringyl (S), or p-ethylphenyl (E) nucleus (1-phenylethanol derivatives) were individually oxidized by MnO2 at a pH of 1.5 and room temperature. The results were compared with those of the corresponding C6-C1-type benzyl alcohol derivatives obtained in our recent report to examine the effect of the presence of the β-methyl group on the oxidation. The presence decelerated the oxidation regardless of the type of aromatic nucleus, although it did not change the order of the oxidation rates: G > S >> H > E. This deceleration results from the steric factor of the β-methyl group in the C6-C2-type compounds. The MnO2 oxidations of the corresponding C6-C2-type compounds deuterated at their α-(benzyl)positions showed that the magnitudes of the kinetic isotope effects are smaller than those observed in the oxidations of the corresponding C6-C1-type compounds, regardless of the type of aromatic nucleus. These smaller magnitudes suggest that the presence of the β-methyl group shifts the initial oxidation mode of MnO2 from direct oxidation of the benzyl position to one-electron oxidation of the aromatic nucleus. Only the S-type compounds afforded products via degradation of the aromatic nuclei.


1974 ◽  
Vol 52 (9) ◽  
pp. 1807-1812 ◽  
Author(s):  
George H. Schmid ◽  
Dennis G. Garratt

The rates of addition and the product compositions have been determined for the addition of 4-chlorobenzenesulfenyl chloride to a series of seven side chain methyl substituted styrenes in 1,1,2,2-tetrachloroethane at 25°. Unlike the addition to the corresponding series of methylated ethylenes, the effect of the methyl groups is not cumulative. The effect of the methyl groups depends upon whether or not the β-methyl group is cis to the phenyl. When it is cis, the rate of addition is decreased compared to styrene and substitution of additional methyl groups has only a small effect on the rate of addition. In compounds lacking a cis-β-methyl group the rate of addition more closely resembles that for addition to the methylated ethylenes. Steric hindrance between the cis-methyl and phenyl groups is believed to be the cause of this difference in behavior between the ethylene and styrene series.


2002 ◽  
Vol 12 (22) ◽  
pp. 3255-3258 ◽  
Author(s):  
Yoshitomo Suhara ◽  
Atsushi Kittaka ◽  
Seishi Kishimoto ◽  
Martin J. Calverley ◽  
Toshie Fujishima ◽  
...  

1992 ◽  
Vol 57 (16) ◽  
pp. 4374-4380 ◽  
Author(s):  
Andrew S. Craig ◽  
Anthony W. Norman ◽  
William H. Okamura

2003 ◽  
Vol 2003 (9) ◽  
pp. 556-558 ◽  
Author(s):  
James R. Hanson ◽  
Peter B. Hitchcock ◽  
Jorge A.R. Salvador

The X-ray crystal structures of some 21-alkylpregnanes have been determined and the effects of a 16α,17α-epoxide and 21-methyl group on the conformation of the side chain are discussed.


1978 ◽  
Vol 89 (2) ◽  
pp. 339-351 ◽  
Author(s):  
Eva Britt Johansson ◽  
Hans Tjälve

ABSTRACT The tissue-disposition and fate of [14C]streptozotocin, labelled in the methyl-group of the N-nitrosomethylurea side-chain, have been studied in mice. Whole-body autoradiography, quantified by densitometric measurements, showed that the pancreatic islets had a high capacity to accumulate radioactivity after the injection of [14C]streptozotocin. Microautoradiography of the pancreas showed that centrally located cells were labelled while peripherally located cells contained a low labelling, indicating a selective labelling of the β-cells. A high radioactivity was present in the liver and the cortex of the kidney at most survival intervals. About 17 % of the radioactivity was exhaled as 14CO2 during 6 h, which shows that the methyl group of the N-nitrosomethylurea side-chain is split off. Radioactivity was shown to be incorporated in the acid-insoluble precipitate of the pancreatic islets, the liver, the kidney, and the exocrine pancreas. This may, to a varying extent, be due both to alkylating reactions and to incorporation of radioactivity in the macromolecules of the tissues via normal metabolic pathways. About 44 % of the radioactivity was excreted as unchanged [14C]streptozotocin in the urine during 24 h, while about 1 % of the radioactivity was found in the faeces. Whole-body autoradiography of [14C]streptozotocin in two Chinese hamsters and one rat also showed a high accumulation of radioactivity in the pancreatic islets in these species.


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