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Dearomatization Reactions of N-Heterocycles Mediated by Group 3 Complexes

Miller, Kevin L. and Williams, Bryan N. and Benitez, Diego and Carver, Colin T. and Ogilby, Kevin R. and Tkatchouk, Ekaterina and Goddard, William A., III and Diaconescu, Paula L. (2010) Dearomatization Reactions of N-Heterocycles Mediated by Group 3 Complexes. Journal of the American Chemical Society, 132 (1). pp. 342-355. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20100329-110010464

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Abstract

Group 3 (Sc, Y, Lu, La) benzyl complexes supported by a ferrocene diamide ligand are reactive toward aromatic N-heterocycles by mediating their coupling and, in a few cases, the cleavage of their C−N bonds. When these complexes reacted with 2,2′-bipyridine or isoquinoline, they facilitated the alkyl migration of the benzyl ligand onto the pyridine ring, a process accompanied by the dearomatization of the N-heterocycle. The products of the alkyl-transfer reactions act as hydrogen donors in the presence of aromatic N-heterocycles, ketones, and azobenzene. Experimental and computational studies suggest that the hydrogen transfer takes place through a concerted mechanism. An interesting disproportionation reaction of the dearomatized, alkyl-substituted isoquinoline complexes is also reported.


Item Type:Article
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http://dx.doi.org/10.1021/ja908489pDOIUNSPECIFIED
http://pubs.acs.org/doi/abs/10.1021/ja908489pPublisherUNSPECIFIED
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2010 American Chemical Society. Received October 13, 2009. Publication Date (Web): December 3, 2009. P.L.D. thanks Prof. James Mayer, University of Washington, Seattle, for a useful suggestion, Dr. Saeed Khan, UCLA, for help with some cyrstallography details, and Dr. Robert Taylor, UCLA, for help with NMR spectroscopy experiments. C.T.C. and K.R.O. thank Mr. Samuel I. Roth, Harvard-Westlake School, for the synthesis of La(CH2C6H5)3(THF)3 and 1La-THF. The experimental work was supported by the UCLA, Sloan Foundation, and NSF (Grant CHE-0847735). The MSC computational facilities were funded by grants from ARO-DURIP and ONR-DURIP. E.T. gratefully acknowledges support from UC MEXUS-CONACyT for a postdoctoral fellowship. D.B., E.T., and W.A.G. were supported partially by the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center funded by the DOE (DE-SC0001298).
Funders:
Funding AgencyGrant Number
UCLAUNSPECIFIED
Sloan FoundationUNSPECIFIED
NSFCHE-0847735
Army Research Office - Defense University Research Instrumentation Program (ARO-DURIP)UNSPECIFIED
Office of Naval Research - Defense University Research Instrumentation Program (ONR-DURIP)UNSPECIFIED
UC MEXUS-CONACyTUNSPECIFIED
Department of Energy (DOE)DE-SC0001298
Issue or Number:1
Record Number:CaltechAUTHORS:20100329-110010464
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20100329-110010464
Official Citation:Dearomatization Reactions of N-Heterocycles Mediated by Group 3 Complexes Kevin L. Miller, Bryan N. Williams, Diego Benitez, Colin T. Carver, Kevin R. Ogilby, Ekaterina Tkatchouk, William A. Goddard III, Paula L. Diaconescu Journal of the American Chemical Society 2010 132 (1), 342-355
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:17811
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:29 Mar 2010 22:21
Last Modified:26 Nov 2019 11:15

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