Af acile and highly chemoselective synthesis of doubly activated cyclopropanes is reported where mixtures of alkenes and b-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,a nd proceeds with av ariety of electronicallydiverse alkenes.C omputational analysis explains the high selectivity observed, which derives from exclusive HOMO to LUMO excitation, instead of free carbene generation. The procedure is operationally simple,u ses no photocatalyst, and provides access in one step to important building blocks for complex molecule synthesis. Scheme 1. Light-mediated reactions of iodonium ylides.
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.
The Generation of doubly activated cyclopropanes upon irradiating alkenes and β‐dicarbonyl‐derived iodonium ylides with visible light from blue LEDs is shown by S. Quideau, W. S. Hopkins, G. K. Murphy, and co‐workers in their Research Article on page 16959 ff. This metal‐free cyclopropane synthesis works with cyclic and acyclic ylides and electronically diverse alkenes. Computational analysis supports a mechanism based on exclusive HOMO to LUMO excitation, instead of free‐carbene generation.
Die Bildung doppelt aktivierter Cyclopropane durch Bestrahlung von Alkenen und β‐Dicarbonyl‐Iodonium‐Yliden mit blauem LED‐Licht wird von S. Quideau, W. S. Hopkins, G. K. Murphy et al. im Forschungsartikel auf S. 17115 beschrieben. Diese metallfreie Cyclopropansynthese aus cyclischen und acyclischen Yliden und elektronisch diversen Alkenen liefert Ausbeuten bis 96 %. Rechnungen bevorzugen einen Mechanismus mit ausschließlicher HOMO‐LUMO‐Anregung gegenüber der Erzeugung freier Carbene.
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