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Article

Second Generation Fluorous DEAD Reagents Have Expanded Scope in the Mitsunobu Reaction and Retain Convenient Separation Features^†

Supporting Info

Sivaraman Dandapani and Dennis P. Curran*

Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260

J. Org. Chem., 2004, 69 (25), pp 8751–8757

DOI: 10.1021/jo0488098

Publication Date (Web): November 12, 2004

†

Dedicated to Professor Robert K. Boeckman, Jr. in celebration of his 60th birthday.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, curran@pitt.edu

Abstract

First generation fluorous DEAD reagent bis(perfluorohexylethyl)azo dicarboxylate (C₆F₁₃(CH₂)₂O₂CNNCO₂(CH₂)₂C₆F₁₃, F-DEAD-1) has been shown to underperform relative to diisopropylazodicarboxylate in difficult Mitsunobu reactions involving hindered alcohols or less acidic pronucleophiles (phenols). Two new second generation fluorous reagents bearing propylene spacers instead of the ethylene spacers show expanded reaction scope while retaining the easy fluorous separation features. Byproducts from “half fluorous” reagent perfluorooctylpropyl tert-butyl azo dicarboxylate (C₈F₁₇(CH₂)₃O₂CNNCO₂^tBu, F-DEAD-2) can be removed by fluorous flash chromatography, and byproducts from bis(perfluorohexylpropyl)azo dicarboxylate (C₆F₁₃(CH₂)₃O₂CNNCO₂(CH₂)₃C₆F₁₃, F-DEAD-3) can be removed by fluorous solid-phase extraction. The new reagents promise to provide general and complementary solutions for separation problems in Mitsunobu reactions without restricting reaction scope.

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History

Published In Issue December 10, 2004
Received July 13, 2004

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Article

Second Generation Fluorous DEAD Reagents Have Expanded Scope in the Mitsunobu Reaction and Retain Convenient Separation Features^†