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comprises alkylamines, pyridines, piperazines, oxadiazoles,
morpholines, benzylamines, and cyclic imines. Other salient
features of this method include: (1) the complete stereo-
retentive hydroxylation of optically active tertiary C−H centers;
(2) the facility of catalyst preparation; (3) the operational
simplicity of the reaction protocol; and (4) the range of
oxidants and acid additives that may be employed without
substantive loss in reaction performance. Mechanistic studies
aimed at elucidating the structure of the active species and
catalyst degradation pathways to inform future catalyst
development are currently underway.
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ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
(8) In spite of its performance with 2a, 1 underperforms considerably
relative to 5 for all other substrates examined.
Experimental details (PDF)
(9) Selectivity for tertiary versus secondary C−H oxidation in 2b is
approximately 13:1 based on statistical correction.
AUTHOR INFORMATION
■
(10) Complex 1 has been reported to catalyze the oxidative cleavage
of aromatic groups, see: Chakraborti, A. K.; Ghatak, U. R. J. Chem. Soc.,
Perkin Trans. 1 1985, 2605.
(11) Reactions with tetrahydroisoquinoline, 4-(3-phenylpropyl)
pyridine and N,N-dimethyl-3-(4-methylpentyl)aniline resulted in
decomposition or recovery of starting material.
(12) The combination of product and recovered starting material for
reactions of 6a, 6b, and 6c totaled 77%, 96%, and 91%, respectively.
(13) No erosion of stereochemical purity occurs if the product
alcohol 3p is resubjected to the reaction conditions, see Supporting
Corresponding Authors
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
(14) (a) Che, C. M.; Wong, K. Y.; Leung, W. H.; Poon, C. K. Inorg.
Chem. 1986, 25, 345. (b) Lau, T. C.; Che, C. M.; Lee, W. O.; Poon, C.
K. J. Chem. Soc., Chem. Commun. 1988, 1406. (c) Che, C. M.; Leung,
W. H.; Li, C. K.; Poon, C. K. J. Chem. Soc., Dalton Trans. 1991, 379.
(15) cis/trans isomerization has been previously noted for these types
of complexes, see: (a) Durham, B.; Wilson, S. R.; Hodgson, D. J.;
Meyer, T. J. J. Am. Chem. Soc. 1980, 102, 600. (b) Dobson, J. C.;
Takeuchi, K. J.; Pipes, D. W.; Geselowitz, D. A.; Meyer, T. J. Inorg.
Chem. 1986, 25, 2357.
This paper is dedicated to Professor Teruaki Mukaiyama on the
occasion of his 90th birthday. We are grateful to Nick Chiappini
(Stanford University) for graciously providing 2k and for
helpful discussions. We thank the National Science Foundation
under the Center for Chemical Innovation in Selective C−H
Functionalization (CHE-1205656) and Novartis Pharmaceut-
icals for financial support of this work.
(16) As rapid ligand loss from cis-[Ru(bpy)2(O)2]2+ has been noted
(see ref 7b), a mono(bpy)Ru(VI) species is also a possible oxidant.
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