Oxidase Catalysis via Aerobically Generated Hypervalent Iodine Intermediates

20 September 2017, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. In particular, oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating oxygen incorporation into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization must overcome the intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents, a broadly useful class of selective two-electron oxidants, from O2. Synthesis of these oxidants is achieved by intercepting reactive intermediates of aldehyde autoxidation. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples a broad array of substrate oxidations to O2 reduction, including olefin functionalization chemistry, carbonyl a-oxidation, oxidative dearomatization, and aerobic C–H amination chemistry.

Keywords

Aerobic Oxidations
Hypervalent Iodine
Oxidase Catalysis
Chemistry

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.