Dearomatization Reactions of N-Heterocycles Mediated by Group 3 Complexes
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.
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).Attached Files
Supplemental Material - ja908489p_si_001.pdf
Supplemental Material - ja908489p_si_002.cif
Files
Name | Size | Download all |
---|---|---|
md5:b6212816a05109672cb331c2ad07022a
|
6.3 MB | Preview Download |
md5:e81ab1c18d3f3ca0f9b3ccbc360431c0
|
286.2 kB | Download |
Additional details
- Eprint ID
- 17811
- Resolver ID
- CaltechAUTHORS:20100329-110010464
- UCLA
- Sloan Foundation
- CHE-0847735
- NSF
- Army Research Office - Defense University Research Instrumentation Program (ARO-DURIP)
- Office of Naval Research - Defense University Research Instrumentation Program (ONR-DURIP)
- UC MEXUS-CONACyT
- DE-SC0001298
- Department of Energy (DOE)
- Created
-
2010-03-29Created from EPrint's datestamp field
- Updated
-
2021-11-08Created from EPrint's last_modified field