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Table 4 Removal of the ketoxime group to give 1,2-amino alcohols
2 (a) F. A. Luzzio, Tetrahedron, 2001, 57, 915; (b) M. T. Reetz, Angew.
Chem., Int. Ed. Engl., 1991, 30, 1531; (c) S. Kobayashi, Y. Mori,
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3 (a) D. M. Hodgson, A. R. Gibbs and G. P. Lee, Tetrahedron, 1996,
52, 14361; (b) A. S. Rao, S. K. Paknikar and J. G. Kirtane, Tetrahedron,
1983, 39, 2323; (c) J. B. Sweeney, Chem. Soc. Rev., 2002, 31, 247;
(d) X. E. Hu, Tetrahedron, 2004, 60, 2701.
4 (a) K. B. Sharpless, A. O. Chong and K. Oshima, J. Org. Chem., 1976,
41, 177; (b) G. Li, H.-T. Chang and K. B. Sharpless, Angew. Chem., Int.
Ed. Engl., 1996, 35, 451; (c) J. A. Bodkim and M. D. McLeod, J. Chem.
Soc., Perkin Trans. 1, 2002, 2733; (d) M. Bruncko, G. Schlingloff and
K. B. Sharpless, Angew. Chem., Int. Ed. Engl., 1997, 36, 1483; (e) G. Liu
and S. S. Stahl, J. Am. Chem. Soc., 2006, 128, 7179.
5 Selected reviews on C–H activations: (a) R. G. Bergman, Nature,
2007, 446, 391; (b) K. Godula and D. Sames, Science, 2006, 312, 67;
(c) D. A. Colby, R. G. Bergman and J. A. Ellman, Chem. Rev., 2010,
110, 624; (d) T. W. Lyons and M. S. Sanford, Chem. Rev., 2010,
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Chem., Int. Ed., 2009, 48, 5094; ( f ) J. Yamaguchi, A. D. Yamaguchi
and K. Itami, Angew. Chem., Int. Ed., 2012, 51, 8960; (g) J. Wencel-
Delford and F. Glorius, Nat. Chem., 2013, 5, 369; (h) D. Y.-K. Chen
and S. W. Youn, Chem. – Eur. J., 2012, 18, 9452; (i) S. H. Cho,
J. Y. Kim, J. Kwak and S. Chang, Chem. Soc. Rev., 2011, 40, 5068;
( j) T. Satoh and M. Miura, Chem. – Eur. J., 2010, 16, 11212;
(k) L. Ackermann, Chem. Rev., 2011, 110, 1315; (l) G. Rouquet and
N. Chatani, Angew. Chem., Int. Ed., 2013, 52, 11726.
6 Selected reviews on C–H aminations: (a) F. Collet, R. H. Dodd and
P. Dauban, Chem. Commun., 2009, 5061; (b) F. Collet, C. Lescot
and P. Dauban, Chem. Soc. Rev., 2011, 40, 1926; (c) J. L. Jeffrey and
R. Sarpong, Chem. Sci., 2013, 4, 4092; (d) T. A. Ramirez, B. Zhao
and Y. Shi, Chem. Soc. Rev., 2012, 41, 931.
7 (a) C. G. Espino and J. Du Bois, Angew. Chem., Int. Ed., 2001, 40, 598;
(b) J. L. Roizen, M. E. Harvey and J. Du Bois, Acc. Chem. Res., 2012,
45, 911; (c) H. Lebel, K. Huard and S. Lectard, J. Am. Chem. Soc.,
1-naphthalenesulfonyl azide resulted in rather lower product yield
(3d). On the other hand, the amidation efficiency in reaction with
alkanesulfonyl azides was observed to be relatively lower (3e–g)
when compared to that with arenesulfonyl analogues.
´
2005, 127, 14198; (d) E. Milczek, N. Boudet and S. Blakey, Angew.
At last, it was demonstrated that the ketoxime directing group,
installed for the iridium-catalyzed C–H bond activation, could be
readily removed to afford b-amino alcohols (Table 4). Upon
screening of various plausible conditions,13 we found that lithium
aluminium hydride (LAH in anhydrous ether solution, 2.5 equiv.)
cleanly removed the ketoxime directing group at room tempera-
ture in excellent yields to furnish the corresponding b-hydroxy
sulfonamides. It is noteworthy that this C–H amidation/N–O bond
cleavage protocol is one of a few examples of highly regioselective
production of 1-amino-2-alcohols.14
In conclusion, we have developed a highly efficient and
selective preparative procedure for 1,2-amino alcohols. The
key step is the Ir-catalyzed direct C–H amidation of sp3 methyl
C–H bonds using organic azides as the amino source under
mild conditions. Various types of alcohols could readily be
employed for the present approach after converting them to
removable directing groups.
Chem., Int. Ed., 2008, 47, 6825; (e) J.-L. Liang, S.-X. Yuan, J.-S. Huang,
W.-Y. Yu and C.-M. Che, Angew. Chem., Int. Ed., 2002, 41, 3465;
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8 (a) J. Ryu, J. Kwak, K. Shin, D. Lee and S. Chang, J. Am. Chem. Soc.,
2013, 135, 12861; (b) K. Shin, Y. Baek and S. Chang, Angew. Chem.,
Int. Ed., 2013, 52, 8031; (c) J. Ryu, K. Shin, S. H. Park, J. Y. Kim and
S. Chang, Angew. Chem., Int. Ed., 2012, 51, 9904; (d) J. Y. Kim,
S. H. Park, J. Ryu, S. H. Cho, S. H. Kim and S. Chang, J. Am. Chem.
Soc., 2012, 134, 9110; (e) H. J. Kim, J. Kim, S. H. Cho and S. Chang,
J. Am. Chem. Soc., 2011, 133, 16382; ( f ) J. Y. Kim, S. H. Cho, J. Joseph
and S. Chang, Angew. Chem., Int. Ed., 2010, 49, 9899; (g) H. Hwang,
J. Kim, J. Jeong and S. Chang, J. Am. Chem. Soc., 2014, 136, 10770.
9 T. Kang, Y. Kim, D. Lee, Z. Wang and S. Chang, J. Am. Chem. Soc.,
2014, 136, 4141.
10 (a) Z. Ren, F. Mo and G. Dong, J. Am. Chem. Soc., 2012, 134, 16991;
(b) F. Mo, J. Tabor and G. Dong, Chem. Lett., 2014, 43, 264.
11 D. Lee, Y. Kim and S. Chang, J. Org. Chem., 2013, 78, 11102.
12 Comparison of relative rates between 1c and 1c-d6 revealed kH/kD
=
10.8, implying that the C–H bond cleavage may be involved in the
rate-limiting step (see the ESI† for details).
13 (a) R. Faragher and T. L. Gilchrist, J. Chem. Soc., Perkin Trans. 1, 1979,
´
249; (b) E. G. Baggiolini, H. L. Lee, G. Pizzolato and M. R. Uskokovic,
Notes and references
1 (a) S. C. Bergmeier, Tetrahedron, 2000, 56, 2561; (b) D. J. Ager,
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I. Prakash and D. R. Schaad, Chem. Rev., 1996, 96, 835; 14 (a) N. Azizi and M. R. Saidi, Org. Lett., 2005, 7, 3649; (b) G. Dequirez,
(c) O. K. Karjalainen and A. M. P. Koskinen, Org. Biomol. Chem.,
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J. Ciesielski, P. Retailleau and P. Dauban, Chem. – Eur. J., 2014,
20, 8929.
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