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Three Roles for the Fluoride Ion in Palladium‐Catalyzed Hiyama Reactions: Transmetalation of [ArPdFL 2 ] by Ar′Si(OR) 3
Author(s) -
Amatore Christian,
Grimaud Laurence,
Le Duc Gaëtan,
Jutand Anny
Publication year - 2014
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.201400956
Subject(s) - transmetalation , chemistry , fluoride , catalysis , reductive elimination , palladium , silicate , medicinal chemistry , ion , kinetic energy , inorganic chemistry , polymer chemistry , organic chemistry , physics , quantum mechanics
From the kinetic data on the transmetalation/reductive elimination in fluoride‐promoted Hiyama reactions, obtained using electrochemical techniques, it has been established that fluoride ions play three roles. F − reacts with trans ‐[ArPdBrL 2 ] (L=PPh 3 ) to form trans ‐[ArPdFL 2 ], which reacts with Ar′Si(OMe) 3 in the rate‐determining transmetalation, whereas trans ‐[ArPdBrL 2 ] does not react with Ar′Si(OMe) 3 . F − reacts with Ar′Si(OMe) 3 to deliver the unreactive silicate Ar′SiF(OMe) 3 − , thus leading to two antagonistic kinetic effects. In addition, F − catalyzes the reductive elimination from intermediate trans ‐[ArPdAr′L 2 ].