Recent Advances in the Selective Oxidative Dearomatization of Phenols to o-Quinones and o-Quinols with Hypervalent Iodine Reagents

Abstract

ortho-Quinones are valuable molecular frameworks with diverse applications across biology, materials, organic synthesis, catalysis, and coordination chemistry. Despite their broad utility, their synthesis remains challenging, in particular via the direct oxidation of readily accessible phenols, due to the need to affect regioselective ortho oxidation coupled with the sensitivity of the resulting o-quinone products. The perspective looks at the emergence of I(V) hypervalent iodine reagents as an effective class of oxidants for regioselective o-quinone synthesis. The application of these reagents in regioselective phenol oxidation to both o-quinones and o-quinols will be discussed, including a recent report from our laboratory on the first method for the oxidation of electron-deficient phenols using a novel nitrogen-ligated I(V) reagent. Also included are select examples of total syntheses utilizing this methodology as well as recent advancements in chiral I(V) reagent design for asymmetric phenol dearomatization.

1 Introduction

2 I(V): Hypervalent Iodine Reagents

3 I(V)-Mediated Dearomatization to o-Quinones

4 Bisnitrogen-Ligated I(V) Reagents: ortho Dearomatization of Electron-Poor Phenols

5 I(V)-Mediated Dearomatization to o-Quinols

6 Conclusion and Outlook

Key words

ortho-quinone - ortho-quinol - phenol dearomatization - hypervalent iodine - I(V) reagent

Publication History

Received: 30 November 2020

Accepted after revision: 15 December 2020

Article published online:
14 January 2021

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