The Conversion of Primary or Secondary Alcohols with Nonaflyl Fluoride into Their Corresponding Inverted Fluorides

Abstract

The present review covers new efficient conversions (fluorodehydroxylations) of aliphatic primary or secondary hydroxy groups with nonaflyl fluoride (n-C₄F₉SO₂F; NfF) and bases such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), diethylamine, triethylamine or triethylamine trihydrofluoride into their corresponding (inverted) fluoro compounds. The scope, mechanisms and side reactions of these combinations of NfF with different bases are discussed.

1 Introduction

2 The Combination of NfF with DBU

3 Mechanism, Optimization and Economics of the NfF/DBU Combination

4 Side Reactions

4.1 Formation of σ-Complexes

4.2 Formation of Olefins

4.3 Interference by Neighboring Nucleophilic Groups

5 Combinations of NfF with Other Bases

6 The Different Mechanisms of Fluorodehydroxylations with NfF

6.1 With DBU

6.2 With Diethylamine

6.3 With Triethylamine or Diisopropylethylamine and Their Corresponding Trihydrofluorides

7 Summary

Key words

fluorodehydroxylation - nonaflyl fluoride - aliphatic fluoro­ compounds - inversion - strong organic bases

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14

The author thanks H.-U. Reissig of this department for quite recently drawing his attention to the review by K. Dax¹³ and thus also to reference 10.

19

In analogy to the ready formation of the rather stable Et₃N·(HF)₃,²⁰ it is assumed that the stronger base DBU, as well as DMAP, N-methylimidazole or diethylamine, likewise add up to three equivalents of HF to form DBU·(HF)_n, DMAP·(HF)_n, Et₂NH·(HF)_n or N-methylimida-zole·(HF)_n for n = 1-3. Yet DBU·(HF)₃, like DMAP·(HF)₃, Et₃N·(HF)₃, Et₂NH·(HF)₃ or N-methylimidazole·(HF)_n can be assumed to form with excess DBU, Et₃N, Et₂NH or DMAP the probably more reactive species DBU·HF, DMAP·HF, Et₃N·HF, Et₂NH·HF or N-methylimidazole·HF!

32

Petrov, O.; et al., unpublished results.

40

The author thanks H. Yamamoto (University of Chicago) for this suggestion.

46

Bennua-Skalmowski, B.; Klar, U.; Vorbrüggen, H. Synthesis 2008, 1175.

51

Lyapkalo, Y. personal communication.

52

Bennua-Skalmowski B., Vorbrüggen H. unpublished results.