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Intramolecular Acetyl Transfer to Olefins by Catalytic C−C Bond Activation of Unstrained Ketones
Author(s) -
Rong ZiQiang,
Lim Hee Nam,
Dong Guangbin
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201711394
Subject(s) - intramolecular force , chemistry , rhodium , carbene , catalysis , bond cleavage , ligand (biochemistry) , reductive elimination , linker , stereochemistry , combinatorial chemistry , hydrogen bond , medicinal chemistry , organic chemistry , molecule , receptor , biochemistry , computer science , operating system
A rhodium‐catalyzed intramolecular acetyl‐group transfer has been achieved through a “cut and sew” process. The challenge arises from the existence of different competitive pathways. Preliminary success has been achieved with unstrained enones that contain a biaryl linker. The use of an electron‐rich N‐heterocycilc carbene (NHC) ligand is effective to inhibit undesired β‐hydrogen elimination. Various 9,10‐dihydrophenanthrene derivatives can be prepared with excellent functional‐group compatibility. The 13 C‐labelling study suggests that the reaction begins with cleavage of the unstrained C−C bond, followed by migratory insertion and reductive elimination.