Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes

A facile and highly chemoselective synthesis of doubly activated cyclopropanes is reported where mixtures of alkenes and β‐dicarbonyl‐derived iodonium ylides are irradiated with light from blue LEDs. This metal‐free synthesis gives cyclopropanes in yields up to 96 %, is operative with cyclic and acy...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-11, Vol.58 (47), p.16959-16965
Main Authors: Chidley, Tristan, Jameel, Islam, Rizwan, Shafa, Peixoto, Philippe A., Pouységu, Laurent, Quideau, Stéphane, Hopkins, W. Scott, Murphy, Graham K.
Format: Article
Language:English
Subjects:
Alkenes
Chemical Sciences
Chemical synthesis
computational analysis
Computer applications
cyclopropanation
Diodes
hypervalent iodine
Intermediates
iodonium ylides
Irradiation
LED photochemistry
Light emitting diodes
Metals
Molecular orbitals
or physical chemistry
Organic chemistry
Organic compounds
Radiation
Selectivity
Theoretical and
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A facile and highly chemoselective synthesis of doubly activated cyclopropanes is reported where mixtures of alkenes and β‐dicarbonyl‐derived iodonium ylides are irradiated with light from blue LEDs. This metal‐free synthesis gives cyclopropanes in yields up to 96 %, is operative with cyclic and acyclic ylides, and proceeds with a variety of electronically‐diverse alkenes. Computational analysis explains the high selectivity observed, which derives from exclusive HOMO to LUMO excitation, instead of free carbene generation. The procedure is operationally simple, uses no photocatalyst, and provides access in one step to important building blocks for complex molecule synthesis. Doubly activated cyclopropanes are generated upon irradiating alkenes and β‐dicarbonyl‐derived iodonium ylides with visible light from blue LEDs. This metal‐free cyclopropane synthesis works with cyclic and acyclic ylides, and with electronically‐diverse alkenes, in yields up to 96 %. Computational analysis supports a mechanism based on exclusive HOMO to LUMO excitation, instead of free carbene generation.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201908994