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Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes
Author(s) -
Chidley Tristan,
Jameel Islam,
Rizwan Shafa,
Peixoto Philippe A.,
Pouységu Laurent,
Quideau Stéphane,
Hopkins W. Scott,
Murphy Graham K.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201908994
Subject(s) - cyclopropanation , diradical , chemistry , carbene , photochemistry , combinatorial chemistry , molecule , metal , organic chemistry , catalysis , physics , nuclear physics , singlet state , excited state
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.