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Reaction of Group III Biheterocyclic Complexes

Carver, Colin T. and Benitez, Diego and Miller, Kevin L. and Williams, Bryan N. and Tkatchouk, Ekaterina and Goddard, William A., III and Diaconescu, Paula L. (2009) Reaction of Group III Biheterocyclic Complexes. Journal of the American Chemical Society, 131 (29). pp. 10269-10278. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20090817-144815760

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Abstract

Group III alkyl complexes supported by a ferrocene diamide ligand (1,1′-fc(NSitBuMe_2)_2) have been found to be reactive toward aromatic N-heterocycles such as 1-methylimidazole and pyridines. These reactions were investigated experimentally and computationally. An initial C−H activation event is followed by a coupling reaction to form biheterocyclic complexes, in which one of the rings is dearomatized. In the case of 1-methylimidazole, the biheterocyclic compound could not be isolated and further led to an imidazole ring-opened product; in the case of pyridines, it transformed into an isomer with extended conjugation of double bonds. Mechanisms for both reactions are proposed on the basis of experimental and computational results. DFT calculations were also used to show that an energetically accessible pathway for the ring-opening of pyridines exists.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja902794wDOIUNSPECIFIED
http://pubs.acs.org/doi/abs/10.1021/ja902794wPublisherUNSPECIFIED
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Diaconescu, Paula L.0000-0003-2732-4155
Additional Information:Copyright © 2009 American Chemical Society. Received April 7, 2009. Publication Date (Web): July 1, 2009. P.L.D. thanks Prof. Jennifer A. Love, University of British Columbia, for a useful suggestion, Dr. Saeed Khan, UCLA, for help with some crystallography details, and Dr. Robert Taylor for help with NMR experiments. D.B. and E.T. thank Dr. Robert J. Nielsen for helpful suggestions. The experimental work was supported by UCLA. The MSC computational facilities were funded by grants from ARO-DURIP and ONR-DURIP. Supporting Information: Experimental details for compound characterizations, DFT calculation details, and full crystallographic descriptions (CIF). This material is available free of charge via the Internet at http://pubs.acs.org.
Funders:
Funding AgencyGrant Number
UCLAUNSPECIFIED
Army Research OfficeUNSPECIFIED
Office of Naval ResearchUNSPECIFIED
Issue or Number:29
Record Number:CaltechAUTHORS:20090817-144815760
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20090817-144815760
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:15104
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:08 Sep 2009 18:00
Last Modified:09 Mar 2020 13:18

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