The support of the National Institutes of Health (R01 GM62541-01) and the National Science Foundation (0116050) is gratefully acknowledged.
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Communication
A Unique Approach to Metal-Induced Bergman Cyclization: Long-Range Enediyne Activation by Ligand-to-Metal Charge Transfer†
Article first published online: 7 DEC 2004
DOI: 10.1002/anie.200461825
Copyright © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Bhattacharyya, S., Pink, M., Baik, M.-H. and Zaleski, J. M. (2005), A Unique Approach to Metal-Induced Bergman Cyclization: Long-Range Enediyne Activation by Ligand-to-Metal Charge Transfer. Angewandte Chemie International Edition, 44: 592–595. doi: 10.1002/anie.200461825
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Publication History
- Issue published online: 11 JAN 2005
- Article first published online: 7 DEC 2004
- Manuscript Received: 30 AUG 2004
Keywords:
- charge transfer;
- cyclization;
- enediynes;
- molybdenum;
- radicals
Graphical Abstract
Dramatic differences are found in the temperatures at which Bergman cyclizations occur when MoIV–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 C2S4 substructure and differential charge repulsion in the transition state lead to a lowering of the barrier to cyclization.