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Palladium‐Catalyzed Directed meta ‐Selective C−H Allylation of Arenes: Unactivated Internal Olefins as Allyl Surrogates
Author(s) -
Achar Tapas Kumar,
Zhang Xinglong,
Mondal Rahul,
Shanavas M. S.,
Maiti Siddhartha,
Maity Sabyasachi,
Pal Nityananda,
Paton Robert S.,
Maiti Debabrata
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201904608
Subject(s) - chemistry , allylic rearrangement , steric effects , olefin fiber , palladium , catalysis , selectivity , stereoselectivity , substrate (aquarium) , functional group , combinatorial chemistry , organic chemistry , medicinal chemistry , oceanography , polymer , geology
Palladium(II)‐catalyzed meta ‐selective C−H allylation of arenes has been developed utilizing synthetically inert unactivated acyclic internal olefins as allylic surrogates. The strong σ‐donating and π‐accepting ability of pyrimidine‐based directing group facilitates the olefin insertion by overcoming inertness of the typical unactivated internal olefins. Exclusive allyl over styrenyl product selectivity as well as E stereoselectivity were achieved with broad substrate scope, wide functional‐group tolerance, and good to excellent yields. Late‐stage functionalisations of pharmaceuticals were demonstrated. Experimental and computational studies shed light on the mechanism and point to key steric control in the palladacycle, thus determining product selectivities.