An Effective Method for Allylic Oxidation of Δ5-Steroids Using tert-Butyl Hydroperoxide

被引：21
作者：
Li, Yuancheng [1 ]
Wu, Xianhong [1 ]
Lee, Tae Bum [1 ]
Isbell, Eleanor K. [1 ]
Parish, Edward J. [1 ]
Gorden, Anne E. V. [1 ]
机构：
[1] Auburn Univ, Dept Chem & Biochem, Coll Sci & Math, Auburn, AL 36849 USA
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2010年 / 75卷 / 05期
关键词：
DIRHODIUM CAPROLACTAMATE; OXYSTEROLS; 7-KETOCHOLESTEROL; LOCALIZATION; ALKENES; REAGENT;
D O I：
10.1021/jo902637k
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
An allylic oxidation method for Delta(5)-steroids using TBHP as oxidant with a 2-quinoxalinol salen Cu(II) complex as catalyst is reported. A variety of Delta(5)-steroidal substrates are selectively oxidized to the corresponding enones. Excellent yields are achieved (up to 99% under optimized conditions) while significantly reducing reaction times required as compared to other current methods.
引用
收藏
页码：1807 / 1810
页数：4
相关论文
共 28 条
[1]   Optimization of the allylic oxidation in the synthesis of 7-keto-Δ5-steroidal substrates [J].
Arsenou, ES ;
Koutsourea, AI ;
Fousteris, MA ;
Nikolaropoulos, SS .
STEROIDS, 2003, 68 (05) :407-414
[2]   Involvement of a calcium-dependent dephosphorylation of BAD associated with the localization of Trpc-1 within lipid rafts in 7-ketocholesterol-induced THP-1 cell apoptosis [J].
Berthier, A ;
Lemaire-Ewing, S ;
Prunet, C ;
Monier, S ;
Athias, A ;
Bessède, G ;
de Barros, JPP ;
Laubriet, A ;
Gambert, P ;
Lizard, G ;
Néel, D .
CELL DEATH AND DIFFERENTIATION, 2004, 11 (08) :897-905
[3]   3,5-dimethylpyrazolium fluorochromate(VI), C5H8N2H[CrO3F], (DmpzHFC):: a convenient new reagent for oxidation of organic substrates [J].
Bora, U ;
Chaudhuri, MK ;
Dey, D ;
Kalita, D ;
Kharmawphlang, W ;
Mandal, GC .
TETRAHEDRON, 2001, 57 (12) :2445-2448
[4]   Optimal TBHP allylic oxidation of Δ5-steroids catalyzed by dirhodium caprolactamate [J].
Choi, Hojae ;
Doyle, Michael P. .
ORGANIC LETTERS, 2007, 9 (26) :5349-5352
[5]   Synthesis of spermidinylcholestanol and spermidinylcholesterol, squalamine analogues [J].
Choucair, B ;
Dherbomez, M ;
Roussakis, C ;
El Kihel, L .
TETRAHEDRON, 2004, 60 (50) :11477-11486
[6]   The impairment of endothelium-dependent arterial relaxation by 7-ketocholesterol is associated with an early activation of protein kinase C [J].
Deckert, V ;
Duverneuil, L ;
Poupon, S ;
Monier, S ;
Le Guern, N ;
Lizard, G ;
Masson, D ;
Lagrost, L .
BRITISH JOURNAL OF PHARMACOLOGY, 2002, 137 (05) :655-662
[7]   Biological effects of oxysterols: Current status [J].
Guardiola, F ;
Codony, R ;
Addis, PB ;
Rafecas, M ;
Boatella, J .
FOOD AND CHEMICAL TOXICOLOGY, 1996, 34 (02) :193-211
[8]  
Guardiola F., 2002, Cholesterol and phytosterol oxydation products: analysis, occurrence, and biological effects
[9]   Oxysterols: functional significance in fetal development and the maintenance of normal retinal function [J].
Javitt, Norman B. .
CURRENT OPINION IN LIPIDOLOGY, 2007, 18 (03) :283-288
[10]   Epalons: 6-substituted derivatives of 7-norepiallopregnanolone [J].
Kasal, A .
TETRAHEDRON, 2000, 56 (22) :3559-3565
123