Journal of the American Chemical Society
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center to a carbocation B3,
which will be rapidly captured by the
2011, 76, 358. (v) Farid, U.; Wirth, T. Angew. Chem. Int. Ed. 2012, 51, 3462. (w)
Mahoney, J. M.; Smith, C. R.; Johnston, J. N. J. Am. Chem. Soc. 2005, 127, 1354.
(x) Zhang, B.; Studer, A. Org. Lett. 2013, 15, 4548.
1
2
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9
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neighboring carbamate group, thereby affording 30. Alternatively,
16
oxidative carboxylate ligand-transfer may directly occur with B2 to
afford the protected amino alcohol 31. We still cannot completely
rule out the possibility that electron-transfer from B2 to the iron
center occurs first and that the oxidation product B4 will then be
(3) For selected references of rhodium nitrenoid-mediated amino-
acetoxylation, see: (a) Levites-Agababa, E.; Menhaji, E.; Perlson, L. N.; Rojas, C.
M. Org. Lett. 2002, 4, 863. (b) Padwa, A.; Stengel, T. Org. Lett. 2002, 4, 2137. (c)
Mulcahy, J. V.; Du Bois, J. J. Am. Chem. Soc. 2008, 130, 12630. (d) Beaumont, S.;
Pons, V.; Retailleau, P.; Dodd, R. H.; Dauban, P. Angew. Chem. Int. Ed. 2010,
49, 1634. (e) Gigant, N.; Dequirez, G.; Retailleau, P.; Gillaizeau, I.; Dauban, P.
Chem.–Eur. J. 2012, 18, 90. (f) Dequirez, G.; Ciesielski, J.; Retailleau, P.; Dauban,
P. Chem.–Eur. J. 2014, 20, 8929. For a manganese-mediated stoichiometric
method, see: (g) Du Bois, J.; Tomooka, C. S.; Hong, J.; Carreira, E. M. J. Am.
3
captured by a carboxylate to deliver 31. When the substituent (R )
has a less significant radical-stabilizing effect, B1 and B2 are relative-
ly short-lived high energy species; therefore, the oxidative neighbor-
ing group participation through B1 may be favored to afford 30.
However, when the substituent has a strong radical-stabilizing effect
and both species are relatively long-lived, the ligand transfer from
the iron center through B2 may become dominant to deliver 31.
Chem. Soc. 1997, 119, 3179.
3
(4) For selected references of rhodium nitrenoid-mediated sp C−H
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
amination, see: (a) Espino, C. G.; Du Bois, J. Angew. Chem. Int. Ed. 2001, 40,
598. (b) Espino, C. G.; Wehn, P. M.; Chow, J.; Du Bois, J. J. Am. Chem. Soc.
In conclusion, we have discovered
a new iron-catalyzed
2
001, 123, 6935. (c) Espino, C. G.; Fiori, K. W.; Kim, M.; Du Bois, J. J. Am. Chem.
Soc. 2004, 126, 15378. (d) Zalatan, D. N.; Du Bois, J. J. Am. Chem. Soc. 2008, 130,
220. (e) Nguyen, Q.; Sun, K.; Driver, T. G. J. Am. Chem. Soc. 2012, 134, 7262.
stereoselective olefin amino-oxygenation method in which a bench-
stable functionalized hydroxylamine is applied as the amination
reagent and the oxidant. This method tolerates a broad range of
synthetically valuable olefins including those that are incompatible
with existing amino-oxygenation methods. It can also provide amino
alcohol building blocks with regio- and stereochemical arrays that
are complementary to known methods. Our preliminary mechanistic
studies revealed that an iron nitrenoid is a possible intermediate and
its enantioselectivity can be controlled by chiral ligands. This
discovery demonstrates the feasibility of developing a unique
approach for iron-catalyzed selective olefin difunctionalization. Our
ongoing efforts focus on understanding the mechanism of this new
reaction and its applications in organic synthesis.
9
For selected references of olefin aziridination through metallonitrenes, see: (f)
Li, Z.; Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326. (g) Evans,
D. A.; Faul, M. M.; Bilodeau, M. T.; Anderson, B. A.; Barnes, D. M. J. Am. Chem.
Soc. 1993, 115, 5328. (h) Müller, P.; Baud, C.; Jacquier, Y. Can. J. Chem. 1998, 76,
738. (i) Noda, K.; Hosoya, N.; Irie, R.; Ito, Y.; Katsuki, T. Synlett 1993, 469. (g)
Au, S. M.; Huang, J. S.; Yu, W. Y.; Fung, W. H.; Che, C. M. J. Am. Chem. Soc.
1999, 121, 9120. (k) Guthikonda, K.; Du Bois, J. J. Am. Chem. Soc. 2002, 124,
13672. (l) Lebel, H.; Lectard, S.; Parmentier, M. Org. Lett. 2007, 9, 4797. (m)
Watson, I. D. G.; Yu, L.; Yudin, A. K. Acc. Chem. Res. 2006, 39, 194. (n) Sub-
barayan, V.; Ruppel, J. V.; Zhu, S.; Perman, J. A.; Zhang, X. P. Chem. Commun.
2009, 4266. (o) Jat, J. L.; Paudyal, M. P.; Gao, H.; Xu, Q.-L.; Yousufuddin, M.;
Devarajan, D.; Ess, D. H.; Kürti, L.; Falck, J. R. Science 2014, 343, 61.
(
5) For selected references of iron-nitrenoid mediated nitrogen atom
transfer, see: (a) Breslow, R.; Gellman, S. H. J. Chem. Soc. Chem. Commun.
982, 1400. (b) Mahy, J. P.; Battioni, P.; Mansuy, D. J. Am. Chem. Soc. 1986, 108,
1079. (c) Nakanishi, M.; Salit, A. F.; Bolm, C. Adv. Synth. Catal. 2008, 350, 1835.
d) Paradine, S. M.; White, M. C. J. Am. Chem. Soc. 2012, 134, 2036. (e) Hen-
ASSOCIATED CONTENT
Supporting Information
1
(
nessy, E. T.; Betley, T. A. Science 2013, 340, 591. (f) Liu, Y.; Guan, X.; Wong, E.
L.-M.; Liu, P.; Huang, J.-S.; Che, C.-M. J. Am. Chem. Soc. 2013, 135, 7194. (g)
Bach, T.; Schlummer, B.; Harms, K. Chem. Commun. 2000, 287. (h) Churchill,
D. G.; Rojas, C. M. Tetrahedron Lett. 2002, 43, 7225. (i) Brown, S. D.; Betley, T.
A.; Peters, J. C. J. Am. Chem. Soc. 2002, 125, 322. (j) Cowley, R. E.; Eckert, N. A.;
Vaddadi, S.; Figg, T. M.; Cundari, T. R.; Holland, P. L. J. Am. Chem. Soc. 2011,
Experimental procedure, characterization data for all new com-
pounds, selected NMR spectra and HPLC traces. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
1
33, 9796.
(6) (a) Liu, G.-S.; Zhang, Y.-Q.; Yuan, Y.-A.; Xu, H. J. Am. Chem. Soc.
013, 135, 3343. (b) Zhang, Y.-Q.; Yuan, Y.-A.; Liu, G.-S.; Xu, H. Org. Lett. 2013,
15, 3910. (c) Lu, D.-F.; Liu, G.-S.; Zhu, C.-L.; Yuan, B.; Xu, H. Org. Lett. 2014, 16,
912.
Corresponding Author
2
2
ACKNOWLEDGMENT
(7) For leading references of chiral BOX and relevant ligands, see: (a)
Evans, D. A.; Woerpel, K. A.; Hinman, M. M.; Faul, M. M. J. Am. Chem. Soc.
1991, 113, 726. (b) Nishiyama, H.; Itoh, Y.; Matsumoto, H.; Park, S.-B.; Itoh, K. J.
Am. Chem. Soc. 1994, 116, 2223. (c) Nishikawa, Y.; Yamamoto, H. J. Am. Chem.
Soc. 2011, 133, 8432.
This work was supported by the National Institutes of Health
(
GM110382), Georgia State University, and the ACS Petroleum Re-
search Fund (ACS PRF 51571-DNI1). We thank Jeffrey Sears for syn-
thesis of a few substrates.
(8) For details of ligand synthesis, see Supporting Information.
(
(
9) For stereochemistry determination, see Supporting Information.
10) For a manganese-mediated glycal aziridination for 2-amino sugar
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(
12) Fe(OTf)
Fe(OTf) led to rapid decomposition of the diene; FeCl
porting Information for details.
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2
/FeCl
2
mixed salts were applied as the catalyst in entry 11.
2
2
was inactive. See Sup-
(
(
(15) Cis/trans isomeric olefins have been observed to present different
7
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2
(
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G.; Forslund, R. E.; Sussman, A. D.; Weerasekera, S. L. J. Am. Chem. Soc. 2010,
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1
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(17) For the evidence for involvement of a possible carbocation inter-
mediate, see eq c of Scheme 2B. For control experiments that exclude the
aziridine as a possible intermediate, see Supporting Information.
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