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Mechanistic Studies of Pd‐Catalyzed Regioselective Aryl CH Bond Functionalization with Strained Alkenes: Origin of Regioselectivity
Author(s) -
Chai David I.,
Thansandote Praew,
Lautens Mark
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201100210
Subject(s) - regioselectivity , chemistry , aryl , palladium , norbornene , alkoxide , catalysis , reductive elimination , stereochemistry , organic chemistry , alkyl , polymer , monomer
Mechanistic studies of a palladium‐catalyzed regioselective aryl CH functionalization of 2‐pyrrole phenyl iodide with norbornene are presented. Kinetic and spectroscopic analyses together with crystallographic data provide evidence for intermediates in a proposed stepwise mechanism. On the basis of the mechanistic studies, the origin of the regioselectivity is due to a ligand exchange between I − and HO − on the norbornyl palladium complex. These mechanistic studies also implicate that either alkoxide or water is responsible for the formation of the palladacycle, but a reversible ring‐opening–ring‐closing process of the palladacycle with HX can retard the rate of reaction of a key intermediate. The significant aspects of the proposed mechanism are discussed in detail.