T. Mitsudome et al. / Tetrahedron Letters 53 (2012) 5211–5214
5213
Table 2 (continued)
Entry
Substrate
Product
Time (h)
16
Conv.b (%)
99
Yieldb (%)
NOH
H
N
8
97 (92)
94 (86)
O
NOH
H
N
9c
16
20
99
98
O
NOH
OH
N
O
10c,d
89 (77)
NOH
O
11
10
8
99
99
97 (91)
98
N
H
NOH
H
N
12
O
a
Reaction conditions: Ti4+-mont (0.1 g), substrate (1.0 mmol), benzonitrile (5 mL), 90 °C, Ar.
Conversions and yields were determined by GC using an internal standard technique. Isolated yields are shown in parentheses.
Substrate (0.5 mmol).
110 °C.
b
c
d
e
Cyclohexanone was formed as a by-product.
NOH
Ti-mont (1.0 g)
Supplementary data
NH
O
benzonitrile (125 mL)
Supplementary data associated with this article can be found, in
90°C, 7 h, Ar
4.9 g
4.8 g
98% isolated yield
(25 mmol)
References and notes
Scheme 1. Beckmann rearrangement of 1 using Ti4+-mont under scale-up reaction
conditions.
1. (a) Gawly, R. E. Org. React. 1988, 35, 1; (b) Smith, M. B.; March, J. Advanced
Organic Chemistry, 5th ed.; John Wiley & Sons: New York, 2001. p 1415.
2. For references of the gas-phase Beckmann rearrangements, see: (a) Yashima,
T.; Oka, N.; Komatsu, T. Catal. Today 1997, 38, 249; (b) Mao, D.; Chen, Q.; Lu, G.
Appl. Catal., A 2003, 244, 273; (c) Izumi, Y.; Ichihashi, H.; Shimazu, Y.; Kitamura,
M.; Sato, H. Bull. Chem. Soc. Jpn. 2007, 80, 1280; (d) Conesa, T. D.; Campelo, J. M.;
O
Ti-mont (0.1 g)
NH
O
Luna, D.; Marinas, J. M.; Romero, A. A. Appl. Catal.,
B 2007, 70, 567; (e)
NH2OH·
HCl (1.2 mmol)
Eickelberg, W.; Hoelderich, W. F. J. Catal. 2009, 263, 42; (f) Cesana, A.; Palmery,
S.; Buzzoni, R.; Spanò, G.; Rivetti, F.; Carnelli, L. Catal. Today 2010, 154, 264; (g)
Nagashima, S.; Kamiguchi, S.; Ohguchi, S.; Chihara, T. Catal. Today 2011, 164,
135.
benzonitrile (5 mL)
90°C, 12 h, Ar
1.0 mmol
95% yield
3. For examples of homogeneous catalysts for the Beckmann rearrangements,
see: (a) Furuya, Y.; Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 2005, 127,
11240; (b) Ramalingan, C.; Park, Y.-T. J. Org. Chem. 2007, 72, 4536; (c)
Hashimoto, M.; Obora, Y.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 2008, 73, 2894; (d)
Liu, L.-F.; Liu, H.; Pi, H.-J.; Yang, S.; Yao, M.; Du, W.; Deng, W.-P. Synth. Commun.
2011, 41, 553.
Scheme 2. One-pot synthesis of 2 from cyclododecanone with hydroxylamine
using Ti4+-mont.
directly converted into 2 in excellent yield in the presence of Ti4+
-
mont and hydroxylamine (Scheme 2).
4. For examples of heterogeneous catalysts for the liquid-phase Beckmann
rearrangement, see: (a) Bosch, A. I.; De la Cruz, P.; Diez-Barra, E.; Loupy, A.;
Langa, F. Synlett 1995, 1259; (b) Ngamcharussrivichai, C.; Wu, P.; Tatsumi, T.
Chem. Lett. 2004, 33, 1288; (c) Li, Z.; Ding, R.; Lu, Z.; Xiao, S.; Ma, X. J. Mol. Catal.
In conclusion, we demonstrated that Ti4+-mont acted as a highly
active heterogeneous catalyst for the liquid-phase Beckmann rear-
rangement under mild reaction conditions. Various ketoximes
including alicyclic, aromatic, and aliphatic ketoximes were suffi-
ciently converted into the corresponding lactams and amides in
high yields. The Ti4+-mont worked well under the scale-up reaction
conditions and the recovered Ti4+-mont was reusable with reten-
tion of its efficiency. Furthermore, the catalytic system using
Ti4+-mont was applicable to the one-pot synthesis of lactams from
ketones through the Beckmann rearrangement.
9
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Acknowledgments
This work was supported by a Grant-in-Aid for Young Scientists
(A) (23686116) from the Japan Society for the Promotion of Science
(JSPS).
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2000, 2, 157.