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DOI: 10.1055/s-0029-1219795
Organocatalytic Mitsunobu Reactions with 3,5-Dinitrobenzoic Acid
Publication History
Publication Date:
23 March 2010 (online)
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Abstract
A second generation procedure for organocatalytic Mitsunobu reactions using 3,5-dinitrobenzoic acid as the pro-nucleophile has been developed. The increased acidity of this acid compared to 4-nitrobenzoic acid, which was used in the original procedure, allowed for higher isolated yields of the desired products and eliminated formation of undesired acetate byproducts.
Key words
3,5-dinitrobenzoic acid - (diacetoxyiodo)benzene - catalytic oxidation - organocatalysis - Mitsunobu reaction
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
General Procedure for Catalytic Mitsunobu Reactions: To a solution of 10 (1.98 mmol) and the alcohol substrate (1.8 mmol) in anhydrous THF (11 mL) under a N2 atmosphere, was added 2 (0.028 mL, 0.18 mmol) and 8 (1.16 g, 3.6 mmol). This was followed by the addition of a solution of 1 (0.94 g, 3.6 mmol) in anhydrous THF (4 mL) slowly by syringe pump (0.25 equiv/h). The reaction mixture was stirred for a total of 16 h and then was diluted with Et2O (30 mL). The organic phase was separated and then washed sequentially with sat. aq NaHCO3 (2 × 20 mL), and brine (20 mL), dried with Na2SO4, filtered and concentrated in vacuo. The crude product was purified by column chromatography. All ester products were characterized by ¹H and ¹³C NMR spectroscopy. Enantiomeric excesses were determined by HPLC. See Supporting Information for details