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Synlett 2006(7): 1055-1058  
DOI: 10.1055/s-2006-939702
LETTER
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Allylic Alkylation of α-Sulfinyl Carbanions under ­Biphasic Conditions

Guillaume Maitro, Guillaume Prestat, David Madec*, Giovanni Poli*
Université Pierre et Marie Curie - Paris 6, Laboratoire de Chimie Organique (UMR CNRS 7611), Institut de Chimie Moléculaire (FR 2769), case 183, 4 place Jussieu, 75252 Paris cedex 05, France
Fax: +33(1)44277567; e-Mail: giovanni.poli@upmc.fr; e-Mail: madec@ccr.jussieu.fr;
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Publication History

Received 23 January 2006
Publication Date:
24 April 2006 (online)

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Abstract

Palladium-catalyzed allylic alkylation of α-sulfinyl carbanions can take place under biphasic conditions. These new conditions provide a simple, mild and efficient route to allylated sulfoxides in good yields. The reaction tolerates a wide variety of EWG groups as additional carbanion stabilizing groups such as ­ester, acetyl, cyano, amide, sulfonyl and sulfinyl functions.

Key words

palladium - sulfoxides - carbanions - catalysis - allylic alkylation

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11

General Procedure for Palladium-Catalyzed Allylic Allylation of α-Sulfinyl Activated Carbanions under Biphasic Conditions. To a solution of [Pd(C3H5)Cl]2 (2 mol%) in CH2Cl2 (500 µL) dppe (5 mol%) was added. After 5 min stirring at r.t., the allyl acetate (1 mmol), a CH2Cl2 (4.5 mL) solution of the sulfoxide (1.1 mmol), H2O (5 mL), and KOH (50% aq solution, 2 mmol) were successively added. The resulting biphasic system was vigorously stirred at r.t. for the indicated reaction time. The aqueous phase was extracted three times with CH2Cl2. The collected organic phases were dried over MgSO4 and the solvent was removed in vacuo. The crude product was purified by flash chromatography.

14

This substrate has been prepared by oxidation of the corresponding thioether with Oxone® and wet alumina (see ref. 8).

20

For pKa values of compounds strictly related to 1f and 1h see: http://www.chem.wisc.edu/areas/reich/pkatable/.