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O
O
O
O
O
OH
OH
Figure 3. ESI-MS/MS-based possible mechanism for the conversion of terminal
double bond into ketonic functionality.
12. Pecchio, M.; Sols, P. N.; Lpez-Prez, L. N.; Vsquez, Y.; Rodrguez, N.; Olmedo, D.;
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3. Ren, J.; Chamberlain, P. P.; Stamp, A.; Short, S. A.; Weaver, K. L.; Romines, K. R.;
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36
mode: ESI(À)-MS(/MS). Reagents, intermediates, and products in
anionic forms were transferred directly from the reaction solution
to the gas phase and then characterized. After 25 min of reaction, a
characteristic ESI-MS (Fig. 1) was recorded.
In the spectrum of Figure 1, a series of anions were detected,
and some anions were identified as key reaction species in their
deprotonated forms: the reactant 4h of m/z 197, m-CBA of m/z
1
4. Ji, H.-B.; Yuan, Q.-L.; Zhou, X.-T.; Pei, L.-X.; Wang, L.-F. Bioorg. Med. Chem. Lett.
2007, 17, 6364.
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19. Mitsudome, T.; Mikami, Y.; Funai, H.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K.
Angew. Chem., Int. Ed. 2008, 47, 138.
1
55, and two intermediates of m/z 211 and m/z 367. The intercep-
20. Mannam, S.; Sekar, G. Tetrahedron Lett. 2008, 49, 2457.
tion of these two key intermediates indicates that the mechanism
involves epoxide formation (m/z 211), followed by epoxide open-
ing via m-CPBA addition (m/z 367).
21. Karimi, B.; Biglari, A.; Clark, J. A.; Budarin, V. Angew. Chem., Int. Ed. 2007, 44,
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2
2. Ishiyama, T.; Kizaki, H.; Hayashi, T.; Suzuki, A.; Miyaura, N. J. Org. Chem. 1998,
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6
ESI-MS/MS (Fig. 2) was then used to characterize these impor-
tant intermediates. The resulting spectra supported the structural
assignments: the anion of m/z 367 undergoes retro-addition either
by losing a neutral m-CPBA to yield the fragment ion of m/z 211
2
3. (a) Ekoue-Kovi, K.; Xu, H.; Wolf, C. Tetrahedron Lett. 2008, 49, 5773; (b)
Polackova, V.; Toma, S.; Augustinova, I. Tetrahedron 2006, 62, 11675; (c) Xin, B.;
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6. Bailey, A. D.; Baru, A. R.; Tasche, K. K.; Mohan, R. S. Tetrahedron Lett. 2008, 49,
2
2
(
the epoxide intermediate), or by losing the neutral epoxide to
2
2
form deprotonated m-CPBA of m/z 155. The epoxide intermediate
of m/z 211 loses mainly CO and then a H to yield the fragment ions
of m/z 183 and m/z 182. Based on the above observations, we pro-
posed a possible mechanism for the conversion of the terminal
double bond into the ketonic functionality as shown in Figure 3.
691.
7. Erdik, E.; Pekel, O. O. J. Organomet. Chem. 2008, 693, 338.
28. Xing, D.; Guan, B.; Cai, G.; Fang, Z.; Yang, L.; Shi, Z. Org. Lett. 2006, 8, 693.
2
9. (a) Cella, R.; Venturoso, R. C.; Stefani, H. A. Tetrahedron Lett. 2008, 49, 16; (b)
Stefani, H. A.; Cella, R.; Vieira, A. S. Tetrahedron 2007, 63, 3623.
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Castellano, E. E.; Emery, F. S.; De Moura, K. C. G.; Pinto, M. C. F. R.; Pinto, A. V.
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3
2
. Conclusion
3
3
1. (a) Borowitz, I. J.; Williams, G. J.; Gross, L.; Rapp, R. J. Org. Chem. 1968, 33, 2013;
(
1
b) Borowitz, I. J.; Gonis, G.; Kelsey, R.; Rapp, R.; Williams, G. J. J. Org. Chem.
966, 31, 3032; (c) Borowitz, I. J.; Gonis, G. Tetrahedron Lett. 1964, 5, 1151.
In summary, we described a simple, fast, and catalyst-free ap-
2. Cella, R.; Cunha, R. L. O. R.; Reis, A. E. S.; Pimenta, D. C.; Klitzke, C. F.; Stefani, H.
proach to the synthesis of benzophenone and ynone systems by
the oxidative cleavage of geminal biaryl ethenes and 1,3-enynes
using m-CPBA under soft reaction conditions. This approach has
the flexibility to introduce the functionalities to the benzophenone
and ynone architectures.
A. J. Org. Chem. 2006, 71, 244.
33. General procedure for the synthesis of 3a–j:
trifluoroborate ethene salt (1) (0.105 g, 0.50 mmol), n-butylaryl telluride (2)
0.5 mmol), Pd(PPh
(0.115 g, 0.1 mmol), triethylamine (0.101 g, 1 mmol),
A suspension of 1-phenyl-1-
(
3 4
)
and silver(I) acetate (0.167 g, 1 mmol) in 5 mL methanol was irradiated in a
water bath of an ultrasonic cleaner for 20 min. Then, the reaction was diluted
with ethyl acetate (30 mL). The organic layer was washed with a saturated
solution of NH
4
Cl (2 Â 10 mL) and water (2 Â 10 mL), dried over MgSO
4
, and
Acknowledgments
concentrated under vacuum. The crude product was purified by flash silica
1
column chromatography using hexane as eluent. (3a) Colorless oil; H NMR
(300 MHz, CDCl
3
) d 5.44 (s, 2H, CH), 7.28–7.35 (m, 10H, ArH); 13C NMR
The authors are grateful to FAPESP (07/59404-2 and 07/51466-
(
1
75.5 MHz, CDCl
3
) d 114.3, 127.7, 128.3, 141.5, 150.1; IR (neat) 1280, 1600,
9
) and CNPq (300613/2007-5) for financial support.
À1
656 cm ; GC/MS: m/z (relative, %) 180 (100), 165 (92), 89 (62).
3
4. General procedure for the synthesis of 4a–j: The solution of 1,1-diarylethene 3
(0.5 mmol) in dichloromethane (5 mL) was placed in a two-necked round-
bottomed flask under nitrogen atmosphere. A solution of m-chloroperbenzoic
acid (0.127 g, 0.75 mmol) in dichloromethane (5 mL) was added dropwise at
À78 °C, and the solution was stirred for 30 min at the same temperature and
for 60–180 min at room temperature. After the completion of the reaction, the
mixture was diluted with chloroform and washed with brine and 10% NaOH
References and notes
1
.
(a) Baggett, S.; Protiva, P.; Mazzola, E. P.; Yang, H.; Ressler, E. T.; Basile, M. J.;
Weinstein, I. B.; Kennelly, E. J. J. Nat. Prod. 2005, 68, 354; (b) Christian, O. M.;
Henry, G. E.; Jacobs, H.; McLean, S.; Reynolds, W. F. J. Nat. Prod. 2001, 64, 23; (c)
Alia, S.; Goundara, R.; Sotheeswarana, S.; Beaulieub, C.; Spinob, C.
Phytochemistry 2000, 53, 281.
solution, then dried with MgSO
4
. The organic layer was evaporated under
vacuum, and the crude product was purified by flash column chromatography
using 20–40% chloroform in hexane.(4a) White solid; mp 50–52 C; H NMR
2
3
.
.
Chiang, Y. –M.; Kuo, Y. -H.; Oota, S.; Fukuyama, Y. J. Nat. Prod. 2003, 66, 1070.
Porto, A. L. M.; Machado, S. M. F.; de Oliveira, C. M. A.; Bittrich, V.; Amaral, M. C.
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J.; Bridi, R.; Dutra-Filho, C. S.; Henriques, A. T.; Poser, G. L. J. Nat. Prod. 2005, 68,
o
1
(
(
1
300 MHz, CDCl ) d 7.41 (t, J = 7.2 Hz, 4H, ArH), 7.52 (t, J = 7.2 Hz, 2H, ArH), 7.74
3
13
d, J = 7.2 Hz, 4H, ArH); C NMR (75.5 MHz, CDCl
3
) d 128.3, 130.1, 132.4, 137.6,
4
.
À1
96.7; IR (KBr) 1659 (CO) cm ; GC–MS (%) 182 (52), 105 (100), 77 (64).
3
5. Singh, F. V.; Weber, M.; Guadagnin, R. C.; Stefani, H. A. Synlett 2008, 1889.
7
84.