376
S. Kang et al. / Tetrahedron Letters 54 (2013) 373–376
1,10-binaphthyl-2,20-dicarboxylic acid 3f is known as an effective
Brønsted acid organocatalyst. In case of acenaphthylene-1,2-dione
1g and aceanthrylene-1,2-dione 1h, the corresponding diacids 3g
and 3h were obtained in high yields (92% and 83%) within 10
and 15 min, respectively (Table 2, entries 7–8).
16. Hui, Y.-Z.; Gai, Y.-H.; Chen, X.-E. Acta Chim. Sin. 1988, 6, 91–94.
17. Yang, D. T. C.; Evans, T. T.; Yamazaki, F.; Narayanna, C.; Kabalka, G. W. Synth.
Commun. 1993, 23, 1183–1187.
18. Yan, J.; Travis, B. R.; Borhan, B. J. Org. Chem. 2004, 69, 9299–9302.
19. (a) Joo, C.; Kang, S.; Kim, S. M.; Han, H.; Yang, J. W. Tetrahedron Lett. 2010, 51,
6006–6007; (b) Kang, S.; Joo, C.; Kim, S. M.; Han, H.; Yang, J. W. Tetrahedron
Lett. 2011, 52, 502–504.
20. Cyclic 1,2-diketones 1 and secondary alcohols 2 were purchased or prepared
according to the literature procedures: Aldrich, 1a, 1e, 1g, 1h, 2a, and 2c; Fluka,
2b; TCI, 2d and 2f; Ref. 25, 1b–d and 1f; Ref. 26, 2e.
While studying the diacid formation upon oxidative cleavage of
cyclic 1,2-diketones, we observed that a
-hydroxy acids 30a, 30c, and
30e were also produced in 5%, 24%, and 22% yields, respectively,
when the reactions of substrates 1a, 1c, and 1e were performed.
21. General procedure for the oxidative cleavage of cyclic 1,2-diketones
1 to
dicarboxylic acids 3: To a solution of cyclic 1,2-diketones 1 (0.5 mmol) and
4,40-dichlorobenzhydrol (1.0 mmol) in distilled THF (10 mL) was added NaH
(60% in mineral oil, 1.5 mmol) at 0 °C. While stirring, the dark-blue solution
was allowed to warm to room temperature. After stirring under O2 (1 atm),
until TLC analysis indicated a complete consumption of the starting material,
the reaction mixture was quenched by adding 0.1 N HCl to a final pH of 1–2
and extracted with CH2Cl2. The combined organic layers were dried over
MgSO4 and concentrated in vacuo. The residue was purified by flash
chromatography (preequilibrated with EtOAc/n-hexane/TFA = 1:20:0.1) to
give 3. All products 3 and 4 were characterized by 1H and 13C NMR spectra,
some of which were compared with the literature data: Aldrich, 3a and 4b; Ref.
27, 3b and 3f; Ref. 28, 4c–f.
However,
a-hydroxy acid was rarely produced when other sub-
strates were employed. Formation of diacid or
a-hydroxy acid
can be explained by the mechanism shown in Figure 1.22 Diacid
3 is formed via the Baeyer–Villiger oxidation mechanism, whereas
a
-hydroxy acid 30 is formed via the benzilic acid rearrangement
mechanism.23 Nucleophilic attack of hydroperoxide 5 and hydrox-
ide 50 on cyclic 1,2-diketone 1 leads to the formation of diacid 3
and a
-hydroxy acid 30, respectively. Hydroperoxide 5 and hydrox-
ide 50 involved are released from the intermediates 20 and 6,
respectively. Regardless of cyclic 1,2-diketone 1 employed, diacid
3 was almost exclusively formed under our reaction conditions.
These results indicate that the nucleophilic attack of hydroperox-
ide 5 on cyclic 1,2-diketone 1 proceeds faster and more efficiently.
This may be due to the higher reactivity of hydroperoxide gener-
ated in situ and in organic solvent.24
Characterization of compound 3c: TLC (MeOH/CH2Cl2 = 1:5) Rf = 0.21; 1H NMR
(400 MHz, DMSO-d6)
d 12.77 (brs, 2H), 7.84 (d, J = 8.4 Hz, 2H), 7.68 (d,
J = 8.4 Hz, 2H), 7.43 (s, 2H); 13C NMR (100 MHz, DMSO-d6) d 166.75, 143.71,
132.52, 131.57, 130.40, 129.30, 124.85; HRMS (EI+) for C14H8Br81BrO4 (M+),
calcd 399.8768, found 399.8764.
Characterization of compound 3d: TLC (MeOH/CH2Cl2 = 1:5) Rf = 0.16; 1H NMR
(600 MHz, DMSO-d6) d 12.47 (brs, 2H), 7.33 (s, 2H), 7.09 (dd, J = 8.4, 2.4 Hz, 2H),
7.05 (d, J = 8.4 Hz, 2H), 3.81 (s, 6H); 13C NMR (150 MHz, DMSO-d6) d 167.96,
157.70, 134.75, 131.93 (2C), 116.57, 114.21, 55.29; HRMS (EI+) for C16H14O6
(M+), calcd 302.0790, found 302.0789.
In summary, we have developed a facile method for the oxida-
tive cleavage of cyclic 1,2-diketones to dicarboxylic acids with
hydroperoxide generated in situ. In situ generation of hydroperox-
ide was effected by the oxidation of 4,40-dichlorobenzhydrol to
4,40-dichlorobenzophenone using NaH under O2 atmosphere. Using
hydroperoxide thus generated in organic solvent enabled such oxi-
dative cleavage to proceed fast and efficiently.
Characterization of compound 3e: TLC (MeOH/CH2Cl2 = 1:6) Rf = 0.28; 1H NMR
(600 MHz, DMSO-d6) d 12.86 (brs, 2H), 8.01 (d, J = 8.4 Hz, 1H), 7.96 (d, J = 8.4
Hz, 1H), 7.94 (d, J = 8.4 Hz, 1H), 7.92 (d, J = 6.0 Hz, 1H), 7.63–7.57 (m, 3H), 7.51
(td, J = 7.8, 1.2 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H), 7.31 (d, J = 7.2 Hz, 1H); 13C NMR
(100 MHz, DMSO-d6) d 169.55, 167.65, 141.13, 137.30, 131.79, 131.13, 131.06,
130.85, 130.47, 130.04, 128.82, 128.07, 127.95, 127.83, 127.74, 127.09, 126.12,
125.03; HRMS (EI+) for C18H12O4 (M+), calcd 292.0735, found 292.0732.
Characterization of compound 3g: TLC (MeOH/CH2Cl2 = 1:7) Rf = 0.31; 1H NMR
(400 MHz, DMSO-d6) d 8.53 (t, J = 7.8 Hz, 4H), 7.91 (t, J = 7.6 Hz, 2H); 13C NMR
(100 MHz, DMSO-d6) d 160.79, 135.47, 132.56, 131.43, 129.78, 127.64, 119.07.
Characterization of compound 3h: TLC (EtOAc/n-hexane = 1:3) Rf = 0.33; 1H NMR
(600 MHz, DMSO-d6) d 9.58 (d, J = 9.0 Hz, 1H), 9.39 (s, 1H), 8.73 (d, J = 9.0 Hz,
1H), 8.70 (d, J = 6.6 Hz, 1H), 8.40 (d, J = 8.4 Hz, 1H), 8.00 (t, J = 7.5 Hz, 1H), 7.93
(t, J = 7.8 Hz, 1H), 7.80 (t, J = 7.5 Hz, 1H); 13C NMR (150 MHz, DMSO-d6) d
160.93, 160.35, 138.50, 136.81, 135.27, 132.90, 132.31, 131.90, 130.68, 130.55,
128.64, 126.94, 126.17, 125.11, 118.89, 111.44.
Acknowledgments
This work was supported by the NRF Grant (No. 2010-0022070)
to H.H. and the NRF WCU program (R31-2008-10029) and the KE-
TEP Human Resources Development Program (20124010203270)
to J.W.Y.
22. Proposed mechanism for the conversion of 2 to 4, see: (a) Lewis, G. E. J. Org.
Chem. 1965, 30, 2433–2436; (b) Wang, X.; Wang, D. Z. Tetrahedron 2011, 67,
3406–3411.
References and notes
23. Kürti, L.; Czakó, B. Strategic Applications of Named Reactions in Organic Synthesis;
Elsevier: New York, 2005. pp. 28–29 and 52–53.
1. Biradar, A. V.; Sathe, B. R.; Umbarkar, S. B.; Dongare, M. K. J. Mol. Catal. A: Chem.
2008, 285, 111–119.
2. Sato, K.; Aoki, M.; Noyori, R. Science 1998, 281, 1646–1647.
24. Following the reviewer0s suggestion, we performed the oxidative cleavage of
cyclic 1,2-diketone 1a (0.5 mmol) using H2O2 (30%, 102 lL, 1.0 mmol) and
NaOH (0.4 N, 2.5 mL, 1.0 mmol) in THF (7.5 mL) at room temperature, which
gave the diacid 3a in 91% yield after 1 h. Note that our new method also gave
the comparable yield within a shorter reaction time (see Table 2, entry 1).
25. For the synthesis and characterization of cyclic 1,2-diketone 1b, see: (a) Park,
T.-H.; Koh, K.; Wong-Foy, A. G.; Matzger, A. J. Cryst. Growth Des. 2011, 11, 2059–
2063; Compound 1c: (b) Kim, H.-J.; Lee, E.; Park, H.-S.; Lee, M. J. Am. Chem. Soc.
2007, 129, 10994–10995; (c) Zhang, J.; Wang, X.; Su, Q.; Zhi, L.; Thomas, A.;
Feng, X.; Su, D. S.; Schlögl, R.; Müllen, K. J. Am. Chem. Soc. 2009, 131, 11296–
11297; Compound 1d: (d) Trosien, S.; Waldvogel, S. R. Org. Lett. 2012, 14,
2976–2979; Compound 1f: (e) Page, P. C. B.; Buckley, B. R.; Farah, M. M.;
Blacker, A. J. Eur. J. Org. Chem. 2009, 3413–3426; (f) Shen, H.-C.; Tang, J.-M.;
Chang, H.-K.; Yang, C.-W.; Liu, R.-S. J. Org. Chem. 2005, 70, 10113–10116; (g)
Furutani, T.; Hatsuda, M.; Imashiro, R.; Seki, M. Tetrahedron: Asymmetry 1999,
10, 4763–4768; (h) Brunner, H.; Goldbrunner, J. Chem. Ber. 1989, 122, 2005–
2009; (i) Modler-Spreitzer, A.; Fritsch, R.; Mannschreck, A. Collect. Czech. Chem.
Commun. 2000, 65, 555–560.
26. For the synthesis and characterization of secondary alcohol 2e, see: Pavia, M.
R.; Lobbestael, S. J.; Nugiel, D.; Mayhugh, D. R.; Gregor, V. E.; Taylor, C. P.;
Schwarz, R. D.; Brahce, L.; Vartanian, M. G. J. Med. Chem. 1992, 35, 4238–4248.
27. For the characterization of dicarboxylic acid 3b, see: (a) Vonlanthen, D.;
Rotzler, J.; Neuburger, M.; Mayor, M. Eur. J. Org. Chem. 2010, 120–133;
Compound 3f: (b) Schlosser, M.; Bailly, F. J. Am. Chem. Soc. 2006, 128, 16042–
16043.
3. de Boer, J. W.; Brinksma, J.; Browne, W. R.; Meetsma, A.; Alsters, P. L.; Hage, R.;
Feringa, B. L. J. Am. Chem. Soc. 2005, 127, 7990–7991.
4. (a) Herrmann, W. A.; Fischer, R. W.; Marz, D. W. Angew. Chem., Int. Ed. Engl.
1991, 30, 1638–1641; (b) Herrmann, W. A.; Fischer, R. W.; Scherer, W.; Rauch,
M. U. Angew. Chem., Int. Ed. Engl. 1993, 32, 1157–1160; (c) Rudolph, J.; Reddy, K.
L.; Chiang, J. P.; Sharpless, K. B. J. Am. Chem. Soc. 1997, 119, 6189–6190; (d)
Yudin, A. K.; Sharpless, K. B. J. Am. Chem. Soc. 1997, 119, 11536–11537.
5. Fujita, M.; Costas, M.; Que, L., Jr. J. Am. Chem. Soc. 2003, 125, 9912–9913.
6. (a) Shing, T. K. M.; Tam, E. K. W.; Tai, V. W.-F.; Chung, I. H. F.; Jiang, Q. Chem.-
Eur. J. 1996, 2, 50–57; (b) Neisius, N. M.; Plietker, B. J. Org. Chem. 2008, 73,
3218–3227; (c) Griffith, W. P.; Shoair, A. G.; Suriaatmaja, M. Synth. Commun.
2000, 30, 3091–3095; (d) Kogan, V.; Quintal, M. M.; Neumann, R. Org. Lett.
2005, 7, 5039–5042; (e) Plietker, B. J. Org. Chem. 2003, 68, 7123–7125.
7. Travis, B. R.; Narayan, R. S.; Borhan, B. J. Am. Chem. Soc. 2002, 124, 3824–3825.
8. Wang, A.; Jiang, H. J. Org. Chem. 2010, 75, 2321–2326.
9. Xing, D.; Guan, B.; Cai, G.; Fang, Z.; Yang, L.; Shi, Z. Org. Lett. 2006, 8, 693–696.
10. (a) Bailey, P. S. Chem. Rev. 1958, 58, 925–1010; (b) Criegee, R. Angew. Chem., Int.
Ed. Engl. 1975, 14, 745–752; (c) Larock, R. C. Comprehensive Organic
Transformations, 2nd ed.; Wiley-VCH: New York, 1999.
p 1213; For the
explosion of gaseous ozone, see: (d) Koike, K.; Inoue, G.; Fukuda, T. J. Chem. Eng.
Jpn. 1999, 32, 295–299.
11. Franz, J. E.; Herber, J. F.; Knowles, W. S. J. Org. Chem. 1965, 30, 1488–1491.
12. (a) Miyamoto, K.; Tada, N.; Ochiai, M. J. Am. Chem. Soc. 2007, 129, 2772–2773;
(b) Miyamoto, K.; Sei, Y.; Yamaguchi, K.; Ochiai, M. J. Am. Chem. Soc. 2009, 131,
1382–1383; (c) Thottumkara, P. P.; Vinod, T. K. Org. Lett. 2010, 12, 5640–5643.
13. Kojima, H.; Takahashi, S.; Hagihara, N. Tetrahedron Lett. 1973, 14, 1991–1994.
14. Nwaukwa, S. O.; Keehn, P. M. Tetrahedron Lett. 1982, 23, 3135–3138.
15. Sawaki, Y.; Foote, C. S. J. Am. Chem. Soc. 1983, 105, 5035–5040.
28. For the characterization of ketones 4c and 4d, see: (a) Bottalico, D.; Fiandanese,
V.; Marchese, G.; Punzi, A. Synthesis 2009, 2316–2318; Compound 4d: (b) Liao,
Y.-X.; Hu, Q.-S. J. Org. Chem. 2010, 75, 6986–6989; Compound 4e: (c) Head, N.
J.; Olah, G. A.; Prakash, G. K. S. J. Am. Chem. Soc. 1995, 117, 11205–11210;
Compounds 4c and 4f: (d) Su, W.; Jin, C. Synth. Commun. 2004, 34, 4249–4256.