Mild Radical Oxidative sp3-Carbon–Hydrogen Functionalization: Innovative Construction of Isoxazoline and Dibenz[b,f]oxepine/azepine Derivatives

Andrea Gini; Olga García Mancheño

doi:10.1055/s-0035-1560908

Synlett, Inhaltsverzeichnis

Synlett 2016; 27(04): 526-539
DOI: 10.1055/s-0035-1560908

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Mild Radical Oxidative sp³-Carbon–Hydrogen Functionalization: Innovative Construction of Isoxazoline and Dibenz[b,f]oxepine/azepine Derivatives

Andrea Gini

^aInstitute for Organic Chemistry, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany

^bStraubing Center of Science for Renewable Resources (WZS), Schulgasse 16, 94315 Straubing, Germany eMail: olga.garcia-mancheno@chemie.uni-regensburg.de

,

Olga García Mancheño*

^aInstitute for Organic Chemistry, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany

^bStraubing Center of Science for Renewable Resources (WZS), Schulgasse 16, 94315 Straubing, Germany eMail: olga.garcia-mancheno@chemie.uni-regensburg.de

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Abstract

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Abstract

Direct carbon–hydrogen bond functionalization has emerged as a powerful synthetic method for the straightforward and modular functionalization of organic molecules. In this account, we described our latest contributions in the area of oxidative sp³-carbon–hydrogen bond functionalization using mild radical oxidants for the construction of structurally important heterocycles. We have developed two new methodologies in which a new class of substrate and an uncommon nucleophilic reagent have been introduced to the existing palette of reaction partners for oxidative carbon–hydrogen functionalization. To achieve these results, the 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) radical and a benzoyl peroxide/copper(I) system have been employed as oxidants for the dehydrogenative one-pot synthesis of N-alkoxycarbonyl-protected isoxazolines from hydroxylamines and for the synthesis of dibenz[b,f]oxepines, dibenzo[b,f]thiepines, and dibenz[b,f]azepines from simple xanthenes, thioxanthenes, and acridanes, respectively.

1 Introduction

2 2,2,6,6-Tetramethylpiperidinyloxyl-Mediated Dehydrogenative Formation and Trapping of Unstable Nitrones: Synthesis of N-Alkoxycarbonyl-Protected Isoxazoline Derivatives

3 Oxidative sp³-Carbon–Hydrogen Bond Functionalization and Ring Expansion with Trimethylsilyldiazomethane: Synthesis of Dibenzoxepines, Dibenzothiepines, and Dibenzazepines

4 Conclusions and Outlook

Key words

carbon–hydrogen functionalization - oxidations - radicals - peroxides - heterocycles

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Referenzen

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