Formation of an Endoperoxide upon Chromium-Catalyzed Allylic Oxidation of a Triterpene by Oxygen

被引：17
作者：
Chung, Abbie [1 ]
Miner, Matthew R. [1 ]
Richert, Kathleen J. [1 ]
Rieder, Curtis J. [1 ]
Woerpel, K. A. [1 ]
机构：
[1] NYU, Dept Chem, New York, NY 10003 USA
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2015年 / 80卷 / 01期
基金：
美国国家科学基金会;
关键词：
N-HYDROXYPHTHALIMIDE; MOLECULAR-OXYGEN; CARBONYL-COMPOUNDS; AEROBIC OXIDATION; ACID; RADICALS; KETONES; PEROXIDES; OLEFINS; HYDROPEROXIDES;
D O I：
10.1021/jo502344x
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The chromium-catalyzed allylic oxidation of triterpene 1 with O-2 and N-hydroxyphthalimide (NHPI, 5 equiv) formed endoperoxide 2 in 76% yield at ambient temperature. Unlike standard allylic oxidations, this oxidation is catalytic in chromium because oxygen, not the chromium reagent, is the oxidant. This oxidation is sensitive to the precise structure of the substrate. The endoperoxide is only formed if ring A is unsaturated and ring C contains an enone. A mechanism is proposed that involves the coupling of two stabilized radicals on rings A and C to form endoperoxide 2.
引用
收藏
页码：266 / 273
页数：8
相关论文
共 64 条
[1]   Synthesis and in Vitro antioxidant activity of glycyrrhetinic acid derivatives tested with the cytochrome P450/NADPH system [J].
Ablise, M ;
Leininger-Muller, B ;
Wong, CD ;
Siest, G ;
Loppinet, V ;
Visvikis, S .
CHEMICAL & PHARMACEUTICAL BULLETIN, 2004, 52 (12) :1436-1439
[2]  
Anderson E., 2012, Patent Appl., Patent No. [WO2012125488A1, 2012125488]
[3]   Selective catalytic oxidation of cyclohexylbenzene to cyclohexylbenzene-1-hydroperoxide:: a coproduct-free route to phenol [J].
Arends, IWCE ;
Sasidharan, M ;
Kühnle, A ;
Duda, M ;
Jost, C ;
Sheldon, RA .
TETRAHEDRON, 2002, 58 (44) :9055-9061
[4]   REACTIONS OF CYCLOHEXENYL HALIDES WITH TRIBUTYLSTANNANE - STEREOELECTRONIC EFFECTS ON SH2 REACTIONS AT HALOGEN [J].
BECKWITH, ALJ ;
WESTWOOD, SW .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1983, 36 (11) :2123-2132
[5]   Synthesis of glycyrrhetinic acid derivatives for the treatment of metabolic diseases [J].
Beseda, Igor ;
Czollner, Laszlo ;
Shah, Priti S. ;
Khunt, Rupesh ;
Gaware, Rawindra ;
Kosma, Paul ;
Stanetty, Christian ;
del Ruiz-Ruiz, Maria Carmen ;
Amer, Hassan ;
Mereiter, Kurt ;
Da Cunha, Thierry ;
Odermatt, Alex ;
Classen-Houben, Dirk ;
Jordis, Ulrich .
BIOORGANIC & MEDICINAL CHEMISTRY, 2010, 18 (01) :433-454
[6]   ACIDITIES AND HOMOLYTIC BOND-DISSOCIATION ENERGIES OF THE ALPHA-C-H BONDS IN KETONES IN DMSO [J].
BORDWELL, FG ;
HARRELSON, JA .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1990, 68 (10) :1714-1718
[7]   Ingold-Fischer ''persistent radical effect'', solvent effect, and metal salt oxidation of carbon-centered radicals in the synthesis of mixed peroxides from tert-butyl hydroperoxide [J].
Bravo, A ;
Bjorsvik, HR ;
Fontana, F ;
Liguori, L ;
Minisci, F .
JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (12) :3849-3857
[8]   Selective Allylic Oxidation of Cyclohexene Catalyzed by Nitrogen-Doped Carbon Nanotubes [J].
Cao, Yonghai ;
Yu, Hao ;
Peng, Feng ;
Wang, Hongjuan .
ACS CATALYSIS, 2014, 4 (05) :1617-1625
[9]   Reactions of δ-carbon radicals generated by 1,5-hydrogen transfer to alkoxyl radicals [J].
Cekovic, Z .
TETRAHEDRON, 2003, 59 (41) :8073-8090
[10]   Toxicarol V 7-Hydroxytoxicarol and related compounds [J].
Clark, EP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1934, 56 :987-991
1234567