Zhang Z,
Gevorgyan V.
*
University of Texas at Dallas, USA
Escape from Hydrofunctionalization: Palladium Hydride-Enabled Difunctionalization of Conjugated Dienes and Enynes.
Angew. Chem. Int. Ed. 2023;
62: e202311848
DOI:
10.1002/anie.202311848
Key words
palladium catalysis - blue LED - palladium hydrides
Significance
The hydropalladation (monofunctionalization) of conjugated dienes and enynes is limited by the amount of molecular complexity that can be installed in a single step. Gevorgyan and Zhang report an effective difuntionalization of conjugated π-systems using blue LEDs to enhance the hydricity of the intermediate palladium hydride species, ultimately merging Pd0/PdII and PdI/PdII reactivities.
Comment
The authors performed deuterium labelling experiments, using deuterated diphenylsilane. Although the addition of silane was beneficial to the yield of the transformation, no deuterium incorporation was observed when employing Ph2SiD2. This result suggests that the Brønsted acid may act as the predominant hydrogen source for Pd–H.
