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Table 2 Scope of tertiary aliphatic aminesa
Notes and references
Entry
1c
TONb
698
887
807
395
844
Substrates
Products
1 (a) B. R. James and D. V. Stynes, J. Chem. Soc., Chem. Commun., 1972,
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K.-I. Sakurai and H. Ogoshi, Organometallics, 1986, 5, 168;
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Chem. Soc., 1991, 113, 5305; (g) J. P. Collman and R. Boulatov, Inorg.
Chem., 2001, 40, 560; (h) M. S. Sanford and J. T. Groves, Angew.
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2006, 128, 8947.
2
3c,d
4e
5
2 (a) Y. Aoyama, Y. Tanaka, T. Fujisawa, T. Watanabe, H. Toi and
H. Ogoshi, J. Org. Chem., 1987, 52, 2555; (b) J. L. Maxwell,
K. C. Brown, D. W. Bartley and T. Kodadek, Science, 1992,
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1993, 115, 1656; (d) J. T. Groves, Z. Gross and M. K. Stern, Inorg.
Chem., 1994, 33, 5065; (e) L. Huang, Y. Chen, G.-Y. Gao and
X. P. Zhang, J. Org. Chem., 2003, 68, 8179; ( f ) H. Thu, G. S. Tong,
J. Huang, S. L. Chan, Q. Deng and C.-M. Che, Angew. Chem., Int. Ed.,
2008, 47, 9747; (g) H. Lu and X. P. Zhang, Chem. Soc. Rev., 2011,
40, 1899; (h) Y. Zhao, H. Dong, Y. Li and X. Fu, Chem. Commun.,
2012, 48, 3506; (i) C. T. To, K. S. Choi and K. S. Chan, J. Am. Chem.
Soc., 2012, 134, 11388; ( j) J.-C. Wang, Z.-J. Xu, Z. Guo, Q.-H. Deng,
C.-Y. Zhou, X.-L. Wan and C.-M. Che, Chem. Commun., 2012,
48, 4299.
6
543
152
340
392
126
7e
8f
9c
N(CH2CH2OH)3
NH(CH2CH2OH)2
10c,g
3 X. Fu and B. B. Wayland, J. Am. Chem. Soc., 2004, 126, 2623.
4 (a) J. Zhang, S. Li, X. Fu and B. B. Wayland, Dalton Trans., 2009,
3661; (b) L. Liu, M. Yu, B. B. Wayland and X. Fu, Chem. Commun.,
2010, 46, 6353.
5 (a) Cytochrome P450 Structure, Mechanisms and Biochemistry, ed.
P. R. Ortiz de Montellano, Kluwer Academic/Plenum, New York,
3rd edn, 2005; (b) F. P. Guengerich, Chem. Res. Toxicol., 2001,
14, 611; (c) B. Meunier, S. P. de Visser and S. Shaik, Chem. Rev.,
2004, 104, 3947; (d) I. G. Denisov, T. M. Makris, S. G. Sligar and
I. Schlichting, Chem. Rev., 2005, 105, 2253.
11c,e
80
37
12h
N(CH2CHQCH2)3
NH(CH2CHQCH2)2
a
Reactions are performed under the optimum conditions (Table 1,
entry 8). GC results. Determined by 1H NMR. 342 TON of iPr2NH
b
c
d
e
f
was obtained. Determined by the formed aldehyde. The yield of
Et2NH was 50 TON. EtOH was used as solvent. 2.0 mmol of
CF3COOH was added.
g
h
6 (a) P. Shannon and T. Bruice, J. Am. Chem. Soc., 1981, 103, 4580;
(b) J. R. L. Smith and D. N. Mortimer, J. Chem. Soc., Chem. Commun.,
1985, 64; (c) E. I. Karasevich, A. M. Khenkin and A. E. Shilov, J. Chem.
Soc., Chem. Commun., 1987, 731; (d) S. Murata, M. Miura and
M. J. Nomura, J. Chem. Soc., Chem. Commun., 1989, 116;
(e) E. Baciocchi, O. Lanzalunga, A. Lapi and L. Manduchi, J. Am.
Chem. Soc., 1998, 120, 5783; ( f ) T. S. Dowers, D. A. Rock, D. A. Rock
and J. P. Jones, J. Am. Chem. Soc., 2004, 126, 8868; (g) K. Nehru,
M. S. Seo, J. Kim and W. Nam, Inorg. Chem., 2007, 46, 293;
(h) B. Chiavarino, R. Cipollini, M. E. Crestoni, S. Fornarini,
F. Lanucara and A. Lapi, J. Am. Chem. Soc., 2008, 130, 3208;
(i) M. Wang, C. Zhou, M. Wong and C.-M. Che, Chem.–Eur. J.,
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W. Nam and S. Fukuzumi, Inorg. Chem., 2011, 50, 11612;
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2011, 2, 2187.
7 (a) S.-I. Murahashi and T. Watanabe, J. Am. Chem. Soc., 1979,
101, 7429; (b) S.-I. Murahashi, T. Maota and K. Yonemura, J. Am.
Chem. Soc., 1988, 110, 8256; (c) S.-I. Murahashi, T. Naota,
N. Miyaguchi and T. Nakato, Tetrahedron Lett., 1992, 33, 6991;
(d) S. Murata, K. Suzuki, A. Tamatani, M. Miura and M. Nomura,
J. Chem. Soc., Perkin Trans. 1, 1992, 1387; (e) S. Mahapatra,
J. A. Halfen and W. B. Tolman, J. Am. Chem. Soc., 1996,
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Table 3 Scope of tertiary anilinesa
Entry
Substrates
Time/h
TONb
1
2
3
4
5
X = H, R = Me
X = OEt, R = Me
X = Br, R = Me
X = Ac, R = Me
X = H, R = Pr
4
6
22
22
6
219
200c
243c
120c
209
a
Reaction conditions: 2.0 mmol of aniline and 1.0 mmol of (TSPP)RhIII
b
stirred at 363 K under 1 atm O2 in MeOH–H2O (10 : 1 (v/v)). GC
c
results. Determined by 1H NMR.
In summary, a green protocol for catalytic oxidative N-dealkyla-
tion of tertiary amines using dioxygen as the oxidant in aqueous
solution is successfully mediated by rhodium(III) porphyrin
complexes. Addition of acid inhibits the deleterious coordina-
tion of the resulting secondary amine to rhodium(III). Trapping
the imminium ion intermediates for functionalization of the sp3
C–H bond adjacent to nitrogen is under further study.
This work was supported by National Science Foundation of
China (Grants 20801002 and 21171012).
8 J. P. Collman, H. J. H. Wang, R. A. Decreau, T. A. Eberspacher and
C. J. Sunderland, Chem. Commun., 2005, 2497.
9 C. C. Au, T. H. Lai and K. S. Chan, J. Organomet. Chem., 2010,
695, 1370.
10 CRC Handbook of Chemistry and Physics, ed. David R. Lide, CRC
Press, Florida, 90th edn, 2010, Section 3.
11 H. K. Hall, Jr, J. Am. Chem. Soc., 1957, 79, 5441; More examples are
listed in the ESI‡.
c
4216 Chem. Commun., 2013, 49, 4214--4216
This journal is The Royal Society of Chemistry 2013