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Ligand Bite Angle‐Dependent Palladium‐Catalyzed Cyclization of Propargylic Carbonates to 2‐Alkynyl Azacycles or Cyclic Dienamides
Author(s) -
Daniels David S. B.,
Jones Alison S.,
Thompson Amber L.,
Paton Robert S.,
Anderson Edward A.
Publication year - 2014
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.201309162
Subject(s) - palladium , regioselectivity , bite angle , ligand (biochemistry) , nucleophile , denticity , chemistry , phosphine , catalysis , stereoselectivity , sulfonamide , stereochemistry , medicinal chemistry , combinatorial chemistry , organic chemistry , crystal structure , biochemistry , receptor
Abstract The regioselectivity of the palladium‐catalyzed cyclization of propargylic carbonates with sulfonamide nucleophiles is critically dependent on the bite angle of the bidentate phosphine ligand. Ligands with small bite angles favor attack on the central carbon atom of an allenylpalladium intermediate to afford cyclic dienamide products, whereas the use of those with large bite angles leads to alkynyl azacycles, with high stereoselectivity. A computational analysis of the reaction pathway is also presented.