Acylation of Nitronates: [3,3]-Sigmatropic Rearrangement of in Situ Generated N-Acyloxy,N-oxyenamines

被引：23
|
作者：
Kokuev, Aleksandr O. [1 ,2 ]
Antonova, Yulia A. [1 ,3 ]
Dorokhov, Valentin S. [1 ,2 ]
Golovanov, Ivan S. [1 ]
Nelyubina, Yulia V. [4 ]
Tabolin, Andrey A. [1 ]
Sukhorukov, Alexey Yu. [1 ]
Ioffe, Sema L. [1 ]
机构：
[1] Russian Acad Sci, ND Zelinsky Inst Organ Chem, Leninsky Prospect 47, Moscow 119991, Russia
[2] DI Mendeleev Univ Chem Technol Russia, Higher Chem Coll, Miusskaya Sq 9, Moscow 125047, Russia
[3] Moscow MV Lomonosov State Univ, Dept Chem, Leninskie Gory 1, Moscow 119991, Russia
[4] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Vavilov Str 28, Moscow 119991, Russia
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 83卷 / 18期
基金：
俄罗斯科学基金会;
关键词：
COPE REARRANGEMENT; ALPHA-OXYGENATION; INDOLE SYNTHESIS; N-OXIDES; ALDEHYDES; CYCLOADDITION; HYDROLYSIS; ION;
D O I：
10.1021/acs.joc.8b01652
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Acylation of nitronates affords alpha-acyloxyoxime derivatives via an umpolung functionalization of the alpha-position. This transformation involves generation of hitherto unknown N-acyloxy,N-oxyenamines and their fast [3,3]-sigmatropic rearrangement driven by the cleavage of the weak N-O bond. The reaction has a broad scope, and it is regioselective in the case of nitronates possessing nonsymmetrically substituted alpha-positions. Application to the formal total synthesis of clausenamide and cis-clausenamide is presented.
引用
收藏
页码：11057 / 11066
页数：10
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