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A Unique Approach to Metal‐Induced Bergman Cyclization: Long‐Range Enediyne Activation by Ligand‐to‐Metal Charge Transfer
Author(s) -
Bhattacharyya Sibaprasad,
Pink Maren,
Baik MuHyun,
Zaleski Jeffrey M.
Publication year - 2005
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.200461825
Subject(s) - enediyne , metal , charge (physics) , ligand (biochemistry) , range (aeronautics) , chemistry , materials science , physics , stereochemistry , quantum mechanics , composite material , organic chemistry , receptor , biochemistry
Dramatic differences are found in the temperatures at which Bergman cyclizations occur when Mo IV –enedithiolate–enediyne complexes are used (see scheme; S: yellow, Mo: red), and this can be directly attributed to a long‐range electronic polarization effect of the metal center. Ligand‐to‐metal charge transfer within the C 2 S 4 substructure and differential charge repulsion in the transition state lead to a lowering of the barrier to cyclization.