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C. Jin et al.
LETTER
(17) General Procedure for the Oxidation of 1a Using
Approach; John Wiley and Sons: Singapore, 2004, 201.
(d) Warren, S. In Organic Synthesis: The Disconnection
Approach; John Wiley and Sons: Singapore, 2004, 330.
(e) Recupero, F.; Punta, C. Chem. Rev. 2007, 107, 3800.
(f) Handbook of C–H Transformation; Dyker, D., Ed.;
Wiley-VCH: Weinheim, 2005.
Ca(ClO)2
To a mortar were added 1a (1 mmol), TEMPO (0.05 mmol),
Co(OAc)2 (0.01 mmol), Ca(ClO)2 (2.5 mmol), and silica gel
(0.3 g). After 0.5 h under solid grinding at r.t., the reaction
was complete (TLC control). The reaction mixture was
dissolved in CH2Cl2 (3 mL). After filtration, the solvent was
evaporated off. The remaining mixture was passed through a
silica gel column to give 2a. White solid; mp 47.8–49.4 °C.
1H NMR (400 MHz, CDCl3): d = 7.74–7.84 (m, 4 H), 7.53–
7.63 (m, 2 H), 7.41–7.52 (m, 4 H). 13C NMR (100 MHz,
CDCl3): d = 196.7, 137.5, 132.3, 130.0, 128.2. MS (EI):
m/z (%) = 182 (100) [M+], 105 (15), 77 (14), 51 (8).
(18) It was suggested that the alkyl hypochlorite is converted to
ketone in an E2-type reaction: (a) Mohrig, J. R.; Nienhulus,
D. M.; Linck, C. F.; Zoeren, C. V.; Fox, B. B.; Mahaffy,
P. G. J. Chem. Educ. 1985, 62, 519. (b) Sakai, A.;
Hendrickson, D. G.; Hendrickson, W. H. Tetrahedron Lett.
2000, 41, 2759. (c) Bright, Z. R.; Luyeye, C. R.;
(2) (a) Rangarajan, R.; Eisenbraun, E. J. J. Org. Chem. 1985, 50,
2435. (b) Rathore, R.; Saxena, N.; Chandrasekaran, S. Synth.
Commun. 1986, 16, 1493. (c) Muzart, J. Tetrahedron Lett.
1987, 28, 3139.
(3) (a) Gannon, S. M.; Krause, J. G. Synthesis 1987, 915.
(b) Li, W. S.; Liu, L. G. Synthesis 1989, 293. (c) Zhao, D.;
Lee, D. G. Synthesis 1994, 915. (d) Shaabani, A.; Lee, D. G.
Tetrahedron Lett. 2001, 42, 5833.
(4) (a) Banik, B. K.; Venkatraman, M. S.; Mukhopadhyay, C.;
Becker, F. F. Tetrahedron Lett. 1998, 39, 7247.
(b) Shaabani, A.; Bazgir, A.; Abdoli, M. Synth. Commun.
2002, 32, 675. (c) Shaabani, A.; Lee, D. G. Synth. Commun.
2003, 33, 1255.
(5) (a) Ishii, Y.; Nakayama, K.; Takeno, M.; Sakaguchi, S.;
Iwahama, T.; Nishiyama, Y. J. Org. Chem. 1995, 60, 3934.
(b) Yang, G.; Zhang, Q.; Miao, H.; Tong, X.; Xu, J. Org.
Lett. 2005, 7, 263.
(6) Lee, N. H.; Lee, C.; Jung, D. S. Tetrahedron Lett. 1998, 39,
1385.
Marie Morton, A. S.; Sedenko, M.; Landolt, R. G.; Bronzi,
M. J.; Bohovic, K. M.; Alex Gonser, M. W.; Lapainis, T. E.;
Hendrickson, W. H. J. Org. Chem. 2005, 70, 684.
(19) It was reported that the oxidation of moderately active
alkylaromatics based on NaOCl with a mechanism involving
the substitution course: (a) Correia, J. J. Org. Chem. 1992,
57, 4555. (b) Clark, J. H.; Grigoropoulo, G.; Scott, K. Synth.
Commun. 2000, 30, 3731.
(7) Dohi, T.; Takenaga, N.; Goto, A.; Fujioka, H.; Kita, Y.
J. Org. Chem. 2008, 73, 7365.
(8) Catino, A. J.; Nichols, J. M.; Choi, H.; Gottipamula, S.;
Doyle, M. P. Org. Lett. 2005, 7, 5167.
(9) Li, H.; Li, Z.; Shi, Z. Tetrahedron 2009, 65, 1856.
(10) Yi, C. S.; Kwon, K. H.; Lee, D. W. Org. Lett. 2009, 11, 1567.
(11) (a) Vogler, T.; Studer, A. Synthesis 2008, 1979.
(b) Ciriminna, R.; Pagliaro, M. Org. Process Res. Dev. 2010,
14, 245.
(12) (a) Lucio Anelli, P. L.; Biffi, C.; Montanari, F.; Quici, S.
J. Org. Chem. 1987, 52, 2559. (b) Semmelhack, M. F.;
Schmid, C. R.; Cortes, D. A.; Chou, C. S. J. Am. Chem. Soc.
1984, 106, 3374. (c) Shibuya, M.; Sato, T.; Tomizawa, M.;
Iwabuchi, Y. Chem. Commun. 2009, 13, 1739. (d) Hirota,
M.; Tamura, N.; Saito, T.; Isogai, A. Carbohydr. Polym.
2009, 78, 330.
(13) In fact, the amount of HClO becomes significant at the pH of
8.3: (a) Montanari, F.; Penso, M.; Quici, S.; Vigano, P.
J. Org. Chem. 1985, 50, 4888. (b) Banfi, S.; Montanari, F.;
Quici, S. J. Org. Chem. 1989, 54, 1850.
(14) (a) Singh, S. J.; Jayaram, R. V. Catal. Commun. 2009, 10,
2004. (b) Marwah, P.; Marwah, A.; Lardy, H. A. Green
Chem. 2004, 6, 570.
(15) TEMPO can react directly with activated hydrocarbons by
hydrogen abstraction: (a) Coseri, S.; Ingold, K. U. Org. Lett.
2004, 6, 1641. (b) Babiarz, J. E.; Cunkle, G. T.; DeBellis,
A. D.; Eveland, D.; Pastor, S. D.; Shum, S. P. J. Org. Chem.
2002, 67, 6831.
(16) For example, a similar mechanism is proposed: Auty, K.;
Gilbert, B. C.; Barry Thomas, C.; Brown, S. W.; Jones,
C. W.; Sanderson, W. R. J. Mol. Catal. A: Chem. 1997, 117,
279.
(20) General Procedures
To a solution of alkylarenes (1 mmol) in CH2Cl2 (3 mL) at
0–5 °C, TEMPO (0.05 mmol) and Co(OAc)2 (0.01 mmol)
were added followed by the quick addition of a sample
containing 3 mmol of aq NaClO at pH 8.3. After 6 h under
magnetic stirring, the reaction was complete (TLC control).
The organic phase is separated, washed with H2O, and dried
over Na2SO4. After filtration, the solvent was evaporated off.
The remaining mixture was passed through a silica gel
column to obtain the pure products.
Compound 2o: pink solid; mp 160.9–162.1 °C. 1H NMR
(400 MHz, CDCl3): d = 8.21 (d, J = 7.8 Hz, 2 H), 7.39–7.68
(m, 6 H), 2.13 (s, 3 H). 13C NMR (100 MHz, CDCl3):
d = 181.4, 169.9, 141.8, 140.6, 134.4, 133.1, 133.0, 131.5,
130.3, 130.0, 129.0, 128.6, 127.7, 126.3, 89.6, 23.6. MS
(EI): m/z (%) = 323 (3) [M+ + 4], 321 (18) [M+ + 2], 319 (27)
[M+], 284 (64), 242 (100), 213 (95), 178 (71). ESI-HRMS:
m/z calcd for C16H12Cl2NO2: 320.0245; found: 320.0226.
(21) Dailey, J. I.; Hays, R. S.; Lee, H.; Mitchell, R. M.; Ries, J. J.;
Landolt, R. G.; Husmann, H. H.; Lockridge, J. B.;
Hendrickson, W. H. J. Org. Chem. 2000, 65, 2568.
(22) Gramscale Preparation of 2a
To a solution of 1a (8.4 g,50 mmol) in CH2Cl2 (150 mL) at
0–5 °C, TEMPO (0.39 g, 2.5 mmol) and Co(OAc)2 (0.12 g,
0.5mmol) were added followed by the quick addition of a
sample containing 150 mmol of aq NaClO at pH 8.3. The
mixture was vigorously stirred for 6 h. The organic phase is
separated and washed with H2O. The solvent was evaporated
off. Purification of the residue by recrystallization gave 2a
(7.98 g, 47.5 mmol, mp 47–49 °C) in 95% yield.
Synlett 2011, No. 10, 1435–1438 © Thieme Stuttgart · New York