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Journal of the American Chemical Society
(9) Metal nitrene C—H aminations: (a) Espino, C. G.; Du Bois,
M.C.W. is grateful to Pfizer and Bristol-Myers Squibb for finan-
J. Rhodium(II)-Catalyzed Oxidative Amination. In Modern Rhodium-
Catalyzed Organic Reactions; Evans, P. A., Ed.; Wiley-VCH: Wein-
heim, 2005; p. 379. (b) Collet, F.; Dodd, R. H.; Dauban, P. Chem.
Commun. 2009, 5061. (c) Müller, P.; Fruit, C. Chem. Rev. 2003, 103,
2905. (d) Huard, K.; Lebel, H. Chem. Eur. J. 2008, 14, 6222. (e) Yu,
X.-Q.; Huang, J.-S.; Zhou, X.-G.; Che, C.-M. Org. Lett. 2000, 2,
2233.
(10) For an example of a preparatively useful iron-nitrene C—H
amination: Paradine, S. M.; White, M. C. J. Am. Chem. Soc. 2012,
134, 2036.
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cial support. M.A.B. is supported by an Illinois Distinguished
Fellowship (2007-2010) and a Harold R. Snyder Fellowship
(2010-2011). S.A.R.’s studies into the streamlining of natural
product synthesis are supported by the NSF under the Center for
Chemical Innovation in Stereoselective C–H Functionalization
(CHE-0943980) and by an Ullyot Graduate Fellowship (2009-
2010). J. Guerra and R. M. Williams are thanked for providing the
(+)-taxusin. We thank Mr. P. Gormisky for checking the experi-
mental procedure in Table 3, entry 6.
9
(11) The few reported approaches using metal heme complexes
have relied upon appending intricate molecular recognition elements
to the ligand framework and the substrate, leading to highly selective,
but non-general reactions: (a) Breslow, R.; Zhang, X.; Huang, Y. J.
Am. Chem. Soc. 1997, 119, 4535. (b) Yang, J.; Gabriele, B.; Belve-
dere, S.; Huang, Y.; Breslow, R. J. Org. Chem. 2002, 67, 5057.
(12) For an elegant example using a carboxylic acid directing
group to coordinate to the ligand of a non-heme Mn complex, see:
Das, S.; Incarvito, C. D.; Crabtree, R. H.; Brudvig, G. W. Science
2006, 312, 1941.
(13) (a) White, M. C.; Doyle, A. G.; Jacobsen, E. N. J. Am.
Chem. Soc. 2001, 123, 7194. (b) Mas-Ballesté, R.; Que, L., Jr. J. Am.
Chem. Soc. 2007, 129, 15964. (c) For stoichiometric use of a non-
heme iron complex to convert benzoic acid to salicylic acid, see:
Makhlynets, O. V.; Das, P.; Taktak, S.; Flook, M.; Mas-Ballesté, R.;
Rybak-Akimova, E. V.; Que, L., Jr. Chem. Eur. J. 2009, 15, 13171
and references therein.
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