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Synlett 2011(7): 891-894  
DOI: 10.1055/s-0030-1259701
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Highly Selective Palladium-Catalyzed Intramolecular Aminonitroxylation of Alkenes

Shujun Chena, Tao Wub, Guosheng Liu*b, Xingliang Zhena
a Department of Chemistry, Changsha University of Science and Technology, Changsha 410114, P. R. of China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: gliu@mail.sioc.ac.cn;
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Publication History

Received 28 October 2010
Publication Date:
08 March 2011 (online)

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Abstract

A palladium-catalyzed intramolecular oxidative aminonitroxylation of unactivated alkenes, in which AgNO3 functioned as a mild nitrate reagent in the presence of PhI(OAc)2, has been developed. Mechanistic studies suggest that this selective aminonitroxylation reaction likely resulted from a new oxidant PhI(ONO2)2 generated in situ from AgNO3 and PhI(OAc)2.

Key words

palladium - alkenes - difunctionalization - silver - aminonitroxylation

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8

The same stereochemical behavior has been reported.4a,b,5b,6

10

The alternative path a in Scheme  [²] is less likely, but cannot be excluded at this moment. This is because the differen-tiation of cis- and trans-aminopalladation is very difficult.

12

The organic layer contained no Ag ion, which was demon-strated by addition of Bu4NCl - no AgCl precipitated from the organic layer.