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Synthesis 2005(10): 1656-1662  
DOI: 10.1055/s-2005-865309
PAPER
© Georg Thieme Verlag Stuttgart · New York

The Chemistry of N,N-Bis(siloxy)enamines, Part 9. [1] A General Method for the Preparation of α-Hydroxy Oximes from Aliphatic Nitro Compounds

Andrey A. Tabolin, Alexey V. Lesiv*, Yulija A. Khomutova, Pavel A. Belyakov, Yuriy A. Strelenko, Sema L. Ioffe*
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prosp. 47, 119991 Moscow, Russian Federation
Fax: +7(095)1355328; e-Mail: iof@ioc.ac.ru;
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Publication History

Received 4 January 2005
Publication Date:
12 April 2005 (online)

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Abstract

A new convenient procedure for the preparation of a variety of α-hydroxy oximes from available aliphatic nitro compounds via intermediate N,N-bis(siloxy)enamines is presented. The mechanism of the key step, the rearrangement of N,N-bis(siloxy)en­amines, is discussed.

Key words

aliphatic nitro compounds - N,N-bis(siloxy)enamines - α-hydroxy oximes - rearrangement - silylation

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18

Our attempts to realize the transformation ANC → 4 as a one-step process (without isolation of BENA) failed because of the conditions needed for steps ANC → 1 and 1 → 4 differ considerably.

21

Attempts to selectively desilylate oximino group in derivatives 4a-i by use of small quantities of MeOH were unsuccessful because the desilylation of both functional groups proceeded with comparable rates.