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Palladium–Borane Cooperation: Evidence for an Anionic Pathway and Its Application to Catalytic Hydro‐/Deutero‐dechlorination
Author(s) -
Kameo Hajime,
Yamamoto Jun,
Asada Ayaka,
Nakazawa Hiroshi,
Matsuzaka Hiroyuki,
Bourissou Didier
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201909675
Subject(s) - borane , palladium , chemistry , catalysis , moiety , aryl , medicinal chemistry , lewis acids and bases , combinatorial chemistry , organic chemistry , alkyl
Metal–Lewis acid cooperation provides new opportunities in catalysis. In this work, we report a new type of palladium–borane cooperation involving anionic Pd 0 species. The air‐stable DPB palladium complex 1 (DPB=diphosphine‐borane) was prepared and reacted with KH to give the Pd 0 borohydride 2 , the first monomeric anionic Pd 0 species to be structurally characterized. The boron moiety acts as an acceptor towards Pd in 1 via Pd→B interaction, but as a donor in 2 thanks to B‐H‐Pd bridging. This enables the activation of C−Cl bonds and the system is amenable to catalysis, as demonstrated by the hydro‐/deutero‐dehalogenation of a variety of (hetero)aryl chlorides (20 examples, average yield 85 %).