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Catalytic Aerobic Generation of Acyliminium Ions through Electron‐Transfer‐Mediated Carbon‐Carbon Bond Activation
Author(s) -
Aubele Danielle L.,
Rech Jason C.,
Floreancig Paul E.
Publication year - 2004
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200303173
Subject(s) - chemistry , nucleophile , catalysis , amide , electron transfer , nucleophilic addition , ion , ring (chemistry) , photochemistry , carbon fibers , bond cleavage , combinatorial chemistry , medicinal chemistry , organic chemistry , materials science , composite number , composite material
Homobenzylic amides and carbamates, upon single‐electron oxidation, undergo mesolytic cleavage reactions to form acyliminium ions. Appending nucleophilic groups to these substrates results in cyclization reactions to form N ‐acylaminals. The N ‐methylquinolinium ion that serves as the photooxidant in these reactions can function as a catalyst when dioxygen is introduced into these reactions, representing a unique method for effecting catalytic, aerobic oxidations. Herein we present a full account of our studies on catalytic aerobic electron‐transfer‐initiated cyclization reactions of homobenzylic amides and carbamates, with particular emphasis on the roles of the amide group, the nucleophilic group, and the functionality in the tether in promoting efficient ring constructions and altering reaction mechanisms.