1159-67-7

Upstream product

• 67-56-1 methanol 
• 19324-98-2 3β,16α-dihydroxy-5α-androstan-17-one diacetate 
• 811-98-3 d⁽⁴⁾-methanol 
• 28507-02-0 16α-bromo-3β-hydroxy-5α-androstan-17-one 
• 481-29-8 Epiandrosterone 
• 10459-24-2 3β,16α-dihydroxy-5α-androstan-17-one 17,17-dimethyl acetal 

Relevant academic research and scientific papers

Autoxidation vs hydrolysis in 16α-acyloxy steroids

Some enolizable α-hydroxy ketones are extremely susceptible to oxidation with traces of air in a reaction vessel. Autoxidation can be used in synthesis of oxo acids or diacids and their derivatives. Yet alkaline hydrolysis of the substrate is possible though under strictly air-free conditions.

Reactions of Enolizable Steroidal 4-En-3-ones and 17-Ones with Hypervalent Iodine

Reaction of the 3-oxo-4-androsten-derivative 1 or 4 with 1.2 eq. of o-iodosylbenzoic acid in methanolic KOH gave the methoxy products, the 4-methoxide 2 or 5 and the 6β-methoxide 3 or 6, along with dehydrated compound, the 4,6-dienone 7 or 8, respectively.Treatment of the 6-methoxide 3 or 6 with trimethylsilyl iodide yielded the 5α-androstane-3,6-dioxo derivative 11 or 12 in high yield.The same hypervalent oxidation of the 17-oxo steroid 15, 18, 21 or 24 using excess iodine and a longer reaction time produced the corresponding 16α-hydroxy-17,17-dimethylacetal 16, 19,22 or 25, which was converted into the 16α-hydroxy-17-one 17, 20, 23 or 26 by treatment with diluted HCl in every case.Keywords - hypervalent iodine oxidation; o-iodosylbenzoic acid; 4-en-3-oxo steroid; 17-oxo steroid; methoxylation; dehydration; 16α-hydroxy-17,17-dimethoxy steroid; 16α-hydroxy-17-oxo steroid; 5α-saturated 3,6-dioxo steroid

Stereoselective hydrolysis of 16α-halo-17-keto steroids and long-range substitution effects on the hydrolysis of 16α-bromo-17-ketones and 2α-bromo-3-ketones

Epimerization of 16α-chloro- (1a), bromo- (1b), and iodo-3β-hydroxy-5-androsten-17-one (1c) by a brief treatment with 0.2 equiv NaOH in aqueous pyridine reached equilibrium between 16α- and 16β-halo ketones. 16α-/16β-Halo ketone ratios at equilibrium were 1.5 for Cl, 1.25 for Br, and 1.0 for I. Kinetic analysis showed that compounds 1a-c were stereoselectively converted to the corresponding 16α-hydroxy derivative 3 by an S(N)2 mechanism, in which the order of the apparent reactivity was Br > I > Cl. The hydrolysis of a number of 16α-bromo-17-ketones and 2α-bromo-3-ketones was carried out. The yields of the corresponding alcohols were found to depend on remote structural features in the steroids.