Synthesis, Characterization, and Reactivity of a Hypervalent‐Iodine‐Based Nitrooxylating Reagent
METADATA ONLY
Loading...
Author / Producer
Date
2020-09-21
Publication Type
Journal Article
ETH Bibliography
yes
Citations
Altmetric
METADATA ONLY
Data
Rights / License
Abstract
Herein, the synthesis and characterization of a hypervalent‐iodine‐based reagent that enables a direct and selective nitrooxylation of enolizable C−H bonds to access a broad array of organic nitrate esters is reported. This compound is bench stable, easy‐to‐handle, and delivers the nitrooxy (‐ONO2) group under mild reaction conditions. Activation of the reagent by Brønsted and Lewis acids was demonstrated in the synthesis of nitrooxylated β‐keto esters, 1,3‐diketones, and malonates, while its activity under photoredox catalysis was shown in the synthesis of nitrooxylated oxindoles. Detailed mechanistic studies including pulse radiolysis, Stern–Volmer quenching studies, and UV/Vis spectroelectrochemistry reveal a unique single‐electron‐transfer (SET)‐induced concerted mechanistic pathway not reliant upon generation of the nitrate radical.
Permanent link
Publication status
published
External links
Editor
Book title
Journal / series
Volume
59 (39)
Pages / Article No.
17162 - 17168
Publisher
Wiley-VCH
Event
Edition / version
Methods
Software
Geographic location
Date collected
Date created
Subject
hypervalent iodine compounds; nitrate esters; photoredox catalysis; pulse radiolysis; spectroelectrochemistry
Organisational unit
03512 - Günther, Detlef / Günther, Detlef
Notes
Funding
168043 - Development of Novel Iron-Catalyzed Oxidative Transformations of Inert C(sp3)-H Bonds (SNF)
169134 - Molecular Approach to Heterogeneous Catalysis (SNF)
192050 - Molecular Approach and Understanding in Heterogeneous Catalysis (SNF)
169134 - Molecular Approach to Heterogeneous Catalysis (SNF)
192050 - Molecular Approach and Understanding in Heterogeneous Catalysis (SNF)
Related publications and datasets
Is original form of: