Pouzar V, Fajkos J
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Prague.
Steroids. 1994 Dec;59(12):696-701. doi: 10.1016/0039-128x(94)90101-5.
A synthesis of (19E)-3 beta,17-dihydroxy-20-oxopregn-5-en-19-al 19-(O-carboxymethyl)oxime (15), is reported. Hydride reduction of ketone 1 gave the (20R)-hydroxy derivative 2 as the main product. Formylation of 2 followed by cleavage of the epoxide ring and mild Jones oxidation afforded aldehyde 6. Oximation with (O-carboxymethyl)hydroxylamine and subsequent methylation yielded methyl ester 8 which was selectively hydrolyzed to alcohol 9 and oxidized to ketone 10. Enolacetylation, epoxidation, and hydrolysis led to the desired 19-(O-carboxymethyl)oxime derivative of 17-hydroxypregnenolone 15.
报道了(19E)-3β,17-二羟基-20-氧代孕甾-5-烯-19-醛19-(O-羧甲基)肟(15)的合成。酮1的氢化物还原以(20R)-羟基衍生物2作为主要产物。2的甲酰化，随后环氧环的裂解和温和的琼斯氧化得到醛6。用(O-羧甲基)羟胺肟化并随后甲基化得到甲酯8，其被选择性水解为醇9并氧化为酮10。烯醇乙酰化、环氧化和水解导致了所需的17-羟基孕烯醇酮19-(O-羧甲基)肟衍生物15。
