Amino steroids - functionalization of position 20 from position 18 in a pregnane system through a Hofmann-Löffler process. predominant formation of 5α-heteroconan-3β-ol

2010 ◽  
Vol 89 (11) ◽  
pp. 993-1000 ◽  
Author(s):  
G. van De Woude ◽  
M. Biesemans ◽  
L. van Hove
Synthesis ◽  
2018 ◽  
Vol 50 (24) ◽  
pp. 4922-4932
Author(s):  
Piotr Borowski ◽  
Marek Stankevič ◽  
Dorota Strzelecka ◽  
Olga Bąk

Reaction of racemic phosphinic acid derivatives with chiral alcohols proceeds with predominant formation of one diastereomer. The highest level of enrichment has been obtained for transesterfication of racemic methyl benzylphenylphosphinate (64% de). The outcome of the reaction depends on both the structure of chiral alcohol and the starting organophosphorus compound. The results strongly suggest that the nature of the observed phenomena is not a classical equilibration of intermediates found in dynamic kinetic resolution process but is a result of a different reactivity of both enantiomers of racemic substrate towards the same chiral nucleophile.


1997 ◽  
Vol 38 (52) ◽  
pp. 8997-9000 ◽  
Author(s):  
Mariko Kitajima ◽  
Mio Nakamura ◽  
Hiromitsu Takayama ◽  
Kazuki Saito ◽  
Joachim Stöckigt ◽  
...  

1956 ◽  
Vol 34 (1) ◽  
pp. 41-53 ◽  
Author(s):  
V. B. Sefton ◽  
D. J. Le Roy

The polymerization of ethylene sensitized by the thermal decomposition of ethyl iodide in the presence of mercury vapor has been studied at 250°, 275°, and 300 °C. C14-labelled ethyl iodide was used in a number of experiments. The increase in the rate of decomposition of ethyl iodide in the presence of ethylene and the formation of butyl iodide are accounted for by equilibrium processes of the type RI + Hg = R + HgI. The important features of the reaction were established from the identity, quantity, and activity of the various products. The predominant formation of olefins is attributed to the isomerization and decomposition of large radicals. Very little of the butane is formed by the combination of ethyl radicals. Radical disproportionation is the most important chain termination step.


Polyhedron ◽  
2015 ◽  
Vol 100 ◽  
pp. 344-350 ◽  
Author(s):  
Elvira I. Musina ◽  
Tatiana I. Wittmann ◽  
Igor D. Strelnik ◽  
Olga E. Naumova ◽  
Andrey A. Karasik ◽  
...  

1971 ◽  
Vol 66 (4) ◽  
pp. 666-678 ◽  
Author(s):  
D. F. Archer ◽  
R. S. Mathur ◽  
N. Wiqvist ◽  
E. Diczfalusy

ABSTRACT The quantitative significance of the de novo synthesis of Δ5- and Δ4-steroids was assessed in the midgestation human foetus. Two midgestation foetuses and two complete foeto-placental units were perfused at 36°C for 120 minutes with 3.0 and 6.0 mCi of [14C] sodium acetate, respectively, and radiochemically homogeneous carbon-14 labelled steroids were isolated from the adrenals, livers and perfusates. Losses throughout the isolation procedure were monitored in all tissues of all experiments by the recovery of tritium labelled internal standards. In the four experiments, a total of 18.0 mCi of [14C] sodium acetate was perfused and a total of 0.17 μCi of pregnenolone, 2.65 μCi of pregnenolone sulphate, 1.07 μCi of dehydroepiandrosterone and 8.64 μCi of dehydroepiandrosterone sulphate were isolated. A total of 12.53 μCi were isolated in the form of these four compounds; 10.13 μCi of this was present in the perfusates. In all, 0.07% of the administered [14C]-sodium acetate was converted to the four Δ5-steroids studied and 0.048% to dehydroepiandrosterone sulphate. Progesterone was isolated from the perfusates and liver extracts, and 17α-hydroxy-progesterone, androstenedione and testosterone from the perfusates. In the four experiments, a total of 0.045 μCi of carbon-14 labelled Δ4-steroids were isolated, predominantly from the perfusates. In all, less than 0.0003% of the perfused [14C] sodium acetate was converted to Δ4-steroids. Thus, almost 300 times more Δ5- than Δ4-steroids were formed. It is concluded that the extensive de novo steroidogenetic processes taking place in the midgestation human foetus lead to the predominant formation of Δ5-steroid sulphates.


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