Improved stereoselective synthesis of 3-methoxy- and 3-benzyloxy-16-hydroxymethyl-13α-estra-1,3,5(10)-trien-17-ol isomers by transfer hydrogenation using chiral Ru catalysts

被引：0

作者：

Kiss, Anita ^{[1
]}

Mernyak, Erzsebet ^{[1
]}

Wolfling, Janos ^{[1
]}

Szollosi, Gyorgy ^{[2
]}

Schneider, Gyula ^{[1
]}

机构：

[1] Univ Szeged, Dept Organ Chem, Dom Ter 8, H-6720 Szeged, Hungary

[2] Univ Szeged, MTA SZTE Stereochem Res Grp, Dom Ter 8, H-6720 Szeged, Hungary

来源：

REACTION KINETICS MECHANISMS AND CATALYSIS | 2018年 / 125卷 / 01期

基金：

匈牙利科学研究基金会;

关键词：

Asymmetric catalysis; Transfer hydrogenation; Ruthenium; Steroid; ASYMMETRIC TRANSFER HYDROGENATION; NEIGHBORING GROUP PARTICIPATION; KETONES; REDUCTION; COMPLEXES; STEROIDS; LIGANDS;

D O I：

10.1007/s11144-018-1453-6

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The Noyori-type (1S,2S)- and (1R,2R)-N-(para-tosyl)-1 ,2-diphenylethylene-1,2-di-amine ligands complexed with ruthenium have been found to be effective catalysts for the regiospecific transfer hydrogenation of 3-methoxy- and 3-benzyloxy-(Z)16-hydroxymethylidene-13 alpha-estra-1,3,5 (10)-trien-17-ones to 3-methoxy- and 3-benzyloxy-16-hydroxymethyl-13 alpha-estra-1,3,5 (10)-trien-17-one diastereomers. The ratio of the diastereomers depends on the catalyst used. Further reduction of the isolated products with NaBH4 in the presence of cerium(III) chloride (Luche reduction conditions) yielded the corresponding diols. In contrast to the previous preparation methods, this two-step simple hydrogenation/reduction protocol afforded all four possible isomers in almost equal amounts.

引用

页码：47 / 53

页数：7

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