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Divergent CH Insertion–Cyclization Cascades of N ‐Allyl Ynamides
Author(s) -
Adcock Holly V.,
Chatzopoulou Elli,
Davies Paul W.
Publication year - 2015
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.201507167
Subject(s) - ketenimine , chemistry , reactivity (psychology) , carbene , pyridine , combinatorial chemistry , stereochemistry , cleavage (geology) , selectivity , bond cleavage , stereoselectivity , catalysis , medicinal chemistry , organic chemistry , medicine , alternative medicine , geotechnical engineering , pathology , fracture (geology) , engineering
Abstract Gold carbene reactivity patterns were accessed by ynamide insertion into a C(sp 3 )H bond. A substantial increase in molecular complexity occurred through the cascade polycyclization of N ‐allyl ynamides to form fused nitrogen‐heterocycle scaffolds. Exquisite selectivity was observed despite several competing pathways in an efficient gold‐catalyzed synthesis of densely functionalized C(sp 3 )‐rich polycycles and a copper‐catalyzed synthesis of fused pyridine derivatives. The respective gold–keteniminium and ketenimine activation pathways have been explored through a structure–reactivity study, and isotopic labeling identified turnover‐limiting CH bond‐cleavage in both processes.