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Synlett 2010(11): 1623-1626  
DOI: 10.1055/s-0030-1258084
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

SmI2-Mediated Reductive Cross-Coupling Reactions of α-Cyclopropyl Nitrones

Olga N. Burchaka, Géraldine Massonb, Sandrine Py*a
a Département de Chimie Moléculaire (SERCO) UMR-5250, ICMG FR-2607, CNRS Université Joseph Fourier, BP 53, 38041 Grenoble Cedex 09, France
Fax: +33(476)635983; e-Mail: sandrine.py@ujf-grenoble.fr;
b Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette Cedex, France
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Publication History

Received 24 February 2010
Publication Date:
11 June 2010 (online)

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Abstract

Three new α-cyclopropyl nitrones have been synthesized as mechanistic probes for reductive cross-coupling reactions of ­nitrones. The α-cyclopropylcarbinyl radical intermediate formed by single electron transfer from SmI2 to these nitrones is not prone to ring opening, due to a unique stabilization by the vicinal N-O-Sm system. Consequently, β-cyclopropyl hydroxylamines could be prepared in high yield from α-cyclopropyl nitrones.

Key words

nitrone - samarium diiodide - reductive coupling reaction - mechanistic probes - cyclopropyl group

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16

General Procedure for the Coupling Reaction of Nitrones 1-3 and Cyclohexanone; Conditions A: To a stirred and carefully deoxygenated solution of nitrone 1-3 (0.20 mmol) and cyclohexanone (0.30 mmol) in anhyd THF (5 mL), a 0.1 M solution of SmI2 (0.44 mmol) was added at -78 ˚C under argon. After 3 h, sat. solutions of Na2S2O3 (5 mL) and NaHCO3 (5 mL), and EtOAc (20 mL) were added. After extraction, the organic phases were washed with brine, dried over Na2SO4, filtered, and concentrated. Column chromatography yielded racemic products 11-13 (EtOAc-pentane, 1:4) and recovered nitrones 1-3 (MeOH-EtOAc, 5:95). Conditions B. The same procedure was used, but degassed H2O (3.20 mmol) was added before SmI2 addition (0.6 mmol).