5
9
1
a) Silveira, C. C.; Mendes, S. R.; Wolf, L.; Martins, G. M.; Von
Mühlen, L. Tetrahedron 2012, 68, 10464–10469; b) Azeredo, J.
B.; Godoi, M.; Martins, G. M.; Silveira, C. C.; Braga, A. L. J.
Org. Chem. 2014, 79, 4125–4130.
a) Dabdoub, M. J.; Silveira, C. C.; Lenardão, E. J.; Guerrero Jr., P.
G.; Viana, L. H.; Kawasoko, C. Y.; Baroni, A. C. M. Tetrahedron
Lett. 2009, 50, 5569–5571; b) Silveira, C. C.; Felix, L. A.; Braga,
A. L.; Kaufman, T. S. Org. Lett. 2005, 7, 3701–3704; c) Silveira,
C. C.; Machado, A.; Braga, A. L.; Lenardão, E. J. Tetrahedron
Lett. 2004, 45, 4077–4080.
1H). ¹³C NMR δ: 114.2, 118.6, 120.2, 121.4, 124.6, 129.8, 130.9,
132.3, 137.5, 138.4, 150.4, 154.2, 158.2. 8-Methyl-4-(phenyl
selenyl)-2H-chromen-2-one (1ai).- mp: 143-144ºC; ¹H NMR δ:
2.45 (s, 3H), 5.9 (s, 1H), 7.2 (t, J = 7.7, 1H), 7.4-7.42 (m, 1H),
7.44-7.48 (m, 2H), 7.49-7.52 (m, 1H), 7.53-7.56 (m, 1H), 7.66-
7.69 (m, 2H). ¹³C NMR δ: 15.7, 112.6, 118.9, 122.6, 123.7, 123.8,
126.6, 130.3, 130.4, 133.5, 137.2, 150.2, 156.6, 159.2. 4-((4-
Chlorophenyl)selenyl)-8-methyl-2H-chromen-2-one (1aj).- mp:
0
1
1
2
1
53-155ºC; ¹H NMR δ: 2.45 (s, 3H), 5.89 (s, 1H), 7.19 (t, J = 7.7,
H), 7.4-7.45 (m, 3H), 7.52 (dd, J = 7.9, 0.7, 1H), 7.59 (d, J = 8.5,
H). ¹³C NMR δ: 15.7, 112.8, 118.8, 121.9, 122.6, 123.8, 126.7,
30.7, 133.7, 137.2, 138.5, 150.2, 155.9, 159.8. 3-Bromo-4-(p-
1
1
1
2
a) Sharpless, K. B.; Lauer, R. F. J. Am. Chem. Soc. 1973, 95,
2
697–2699; b) Kissane, M.; Murphy, M.; O’Brien, E.; Chopra, J.;
tolylselenyl)-2H-chromen-2-one (1bc).- mp: 104-106ºC. ¹H
NMR δ: 2.30 (s, 3H), 7.05-7.09 (m, 2H), 7.16 (ddd, J = 8.1, 7.3,
Murphy, L.; Collins, S. G.; Lawrence, S. E.; Maguire, A. R. Org.
Biomol. Chem. 2011, 9, 2452–2472.
a) Bovonsombat, P.; Ali, R.; Khan, C.; Leykajarakul, J.; Pla-on,
K.; Aphimanchindakul, S.; Pungcharoenpong, N.; Timsuea, N.;
Arunrat, A.; Punpongjareorn, N. Tetrahedron 2010, 66, 6928–
1
(
.2, 1H), 7.3 (ddd, J = 8.3, 1.2, 0.4, 1H), 7.33-7.36 (m, 2H), 7.49
ddd, J = 8.3, 7.3, 1.5, 1H), 7.94 (ddd, J = 7.7, 1.5, 0.4, 1H). ¹³C
NMR δ: 21.1, 116.9, 120.4, 120.8, 124.8, 125.8, 130.0, 130.6,
32.0, 132.7, 138.6, 150.6, 151.6, 155.6. 3-Bromo-4-((4-chloro
phenyl)selenyl)-8-methyl-2H-chromen-2-one (1bj).- mp: 159-
1
6
935; b) Singh, P. P.; Thatikonda, T.; Kumar, K. A. A.; Sawant, S.
D.; Singh, B.; Sharma, A. K.; Sharma; Singh, D.; Vishwakarma,
R. A. J. Org. Chem. 2012, 77, 5823–5828.
1
8
8
1
61ºC; ¹H NMR δ: 2.46 (s, 3H), 7.1 (t, J = 8.1, 1H), 7.22 (d, J =
.7, 2H), 7.36 (d, J = 8.7, 2H), 7.37-7.39 (m, 1H), 7.77 (ddd, J =
.1, 1.5, 0.6, 1H). ¹³C NMR δ: 15.6, 120.4, 121.1, 124.5, 126.6,
27.8, 129.9, 133.5, 133.7, 134.5, 149.9 (2C), 155.6. 3-Bromo-8-
1
3
a) Kym, P. R.; Iyengar, R.; Souers, A. J.; Lynch, J. K.; Judd, A. S.;
Gao, J.; Freeman, J.; Mulhern, M.; Zhao, G.; Vasudevan, A.;
Wodka, D.; Blackburn, C.; Brown, J.; Che, J. L.; Cullis, C.; Lai, S.
J.; LaMarche, M. J.; Marsilje, T.; Roses, J.; Sells, T.; Geddes, B.;
Govek, E.; Patane, M.; Fry, D.; Dayton, B. D.; Brodjian, B.; Falls,
D.; Brune, M.; Bush, E.; Shapiro, R.; Knourek-Segel, V.; Fey, T.;
McDowell, C.; Reinhart, G. A.; Preusser, L. C.; Marsh, K.;
Hernández, L.; Sham, H. L.; Collins, C. A. J. Med. Chem. 2005,
methyl-4-(p-tolylselenyl)-2H-chromen-2-one (1bk).- mp: 115-
1
7
1
1
18ºC; ¹H NMR δ: 2.29 (s, 3H), 2.45 (s, 3H), 7.03-7.07 (m, 3H),
.32-7.35 (m, 3H), 7.81 (d, J = 8.1, 1H). ¹³C NMR δ: 15.5, 21.1,
20.3, 120.7, 124.3, 126.0, 126.4, 127.9, 130.6, 132.7, 133.4,
38.4, 149.9, 150.8, 155.7. 4-(Phenylselenyl)-3-(phenylthio)-2H-
chromen-2-one (1ca).- mp: 113-116ºC; ¹H NMR δ: 7.09 (ddd, J =
.2, 7.3, 1.2, 1H), 7.18-7.29 (m, 7H), 7.32-7.34 (m, 2H), 7.4-7.46
m, 3H), 7.84 (ddd, J = 8.1, 1.5, 0.4, 1H). ¹³C NMR δ: 116.9,
4
8, 5888–5891; b) Zhao, P.-L.; Wang, L.; Zhu, X.-L.; Huang, X.;
Zhan, C.-G.; Wu, J.-W.; Yang, G.-F. J. Am. Chem. Soc. 2010, 132,
85–194.
8
(
1
1
20.6, 124.3, 127.2, 128.0, 129.1, 129.6, 129.8 (2C), 130.2, 130.8,
1
1
4
5
a) Ren, J.-L.; Zhang, X.-Y.; Yu, B.; Wang, X.-X.; Shao, K.-P.;
Zhu, X.-G.; Liu, H.-M. Eur. J. Med. Chem. 2015, 93, 321–329; b)
Bartlett, M. J.; Turner, C. A.; Harvey, J. E. Org. Lett. 2013, 15,
1
32.0, 132.3, 134.5, 152.4, 155.1, 157.0. 4-((4-Chlorophenyl)
selenyl)-3-(phenylthio)-2H-chromen-2-one (1cb).- mp: 132-
1
2
7
1
1
1
34ºC; ¹H NMR δ: 7.17 (ddd, J = 8.1, 7.3, 1.2, 1H), 7.21-7.25 (m,
H), 7.25-7.28 (m, 1H), 7.28-7.3 (m, 1H), 7.31-7.32 (m, 1H),
.32-7.35 (m, 3H), 7.37 (d, J = 8.7, 2H), 7.45 (ddd, J = 8.3, 7.3,
.5, 1H), 7.85 (ddd, J = 8.2, 1.5, 0.4, 1H). ¹³C NMR δ: 117.0,
20.5, 124.5, 127.3, 128.8, 129.2, 129.6, 129.9, 130.0, 132.2,
33.7, 134.3, 134.4, 152.4, 154.2, 156.8.
2
430–2433; c) Gao, W.-T.; Hou, W.-D.; Zheng, M.-R.; Tang, L.-J.
Synth. Commun. 2010, 40, 732–738.
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1
6, 6181–6184; c) Reddy Parumala, S. K.; Krishna Peddinti, R.
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2
2
Kobayashi, N.; Furuyama, T.; Satoh, K. J. Am. Chem. Soc. 2011,
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1
6
7
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2
2
3
4
1
1
6
7
Denmark, S. E.; Montgomery, J. I. J. Org. Chem. 2006, 71, 6211–
220.
Typical procedure: NaBH
6
4
(19 mg, 0.5 mmol) was added to the
diselenide (0.275 mmol) dissolved in EtOH-THF (4:1 v/v, 2.5 mL)
and the reaction was stirred under argon until it became colorless
6
699.
(
diselenide cleavage). Then, a THF solution of the tosylate (0.5
mmol, 2 mL) was added and the reaction was stirred at r.t. for 30
min. H O was added and the products were extracted with EtOAc
3 × 10 mL). The extract was dried (MgSO ) and concentrated in
2
2
5
6
a) Lubineau, A.; Bienayme, H.; Le Gallic, J. J. Chem. Soc., Chem.
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c) Hirokane, T.; Hirata, Y.; Ishimoto, T.; Nishii, K.; Yamada, H.
Nat. Commun. 2014, 5, 3478.
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S. S. Toxicol. Pathol. 2013, 41, 315–321; c) Elfarra, A. A.;
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Toxicity and Potential New Therapeutic Applications. In:
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USA, 2008. Chapter 3, pp. 57–68.
a) Uher, R.; Mors, O.; Rietschel, M.; Rajewska-Rager, A; Petrovi,
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3
The tissue was incubated with DCHF-DA (1 mM) and NaN in
Tris-HCl buffer (10 mM pH 7.4). The fluorescence was measured
at 520 nm, exciting at 488 nm. Results are in fluorescence units.
2
(
4
vacuo. The residue was purified by column chromatography.
Harrison, P. A.; Murtagh, L.; Willis, C. L. J. Chem. Soc. Perkin
Trans. 1 1993, 3047–3050.
Grayson, D. H.; Lyons, R. G.; Rasool, S. Proceed. Royal Irish
Acad. B 1989, 89B, 167–172.
a) Santoro, S.; Battistelli, B.; Testaferri, L.; Tiecco, M.; Santi, C.
Eur. J. Org. Chem. 2009, 4921–4925; b) Kim, Y.; Mulay, S. V.;
Choi, M.; Yu, S. B.; Jon, S. Churchill, D. G. Chem. Sci. 2015, 6,
1
1
2
8
9
0
2
7
5
435–5439.
Mp and NMR data of selected compounds (400 MHz, in CDCl
-(Phenylselenyl)-2H-chromen-2-one (1aa).- mp: 145-146ºC; ¹H
NMR δ: 5.91 (s, 1H), 7.29-7.34 (m, 2H), 7.44-7.49 (m, 2H), 7.5-
.53 (m, 1H), 7.56 (ddd, J = 8.5, 7.3, 1.5, 1H), 7.66-7.71 (m, 3H).
³C NMR δ: 112.9, 117.1, 119.2, 123.5, 124.2, 125.0, 130.4 (2C),
2
1
3
):
4
7
¹
2
2
8
9
1
2
1
7
32.2, 137.2, 151.8, 156.1, 159.0. 4-((4-Chlorophenyl)selenyl)-
H-chromen-2-one (1ab).- mp: 148-149ºC; ¹H NMR δ: 5.89 (s,
H), 7.29-7.35 (m, 2H), 7.44 (d, J = 8.6, 2H), 7.56 (ddd, J = 8.5,
.4, 1.5, 1H), 7.60 (d, J = 8.6, 2H), 7.67 (dd, J = 7.9, 1.4, 1H). ¹³C
NMR δ: 113.3, 117.2, 119.1, 121.7, 124.3, 124.9, 130.8, 132.4,
37.3, 138.4, 151.9, 155.4, 158.9. 4-(Benzylselenyl)-2H-chromen
2-one (1ad).- mp: 150-153ºC; ¹H NMR δ: 4.29 (s, 2H), 6.46 (s,
1
-
1
7
H), 7.22-7.27 (m, 1H), 7.29-7.36 (m, 4H), 7.39-7.42 (m, 2H),
.52 (ddd, J = 8.6, 7.3, 1.5, 1H), 7.59 (dd, J = 7.9, 1.4, 1H). ¹³C
30 Halliwell, B.; Gutteridge, J. M. C. Free Radical Biol.Med. 1995,
18, 125–126.
31 Wang, X.; Michaelis, E. K. Front. Aging Neurosci. 2010, 2, 9–12.
32 Okawa, N.; Ohiahi, K. Yagi, Anal. Biochem. 1979, 95, 351–358.
NMR δ: 30.6, 112.8, 117.2, 119.5, 124.2, 125.3, 127.9, 128.9,
29.1, 132.1, 134.8, 151.9, 154.5, 158.7. 6-Chloro-4-((4-chloro
1
phenyl)selenyl)-2H-chromen-2-one (1af).- mp: 164-166ºC; ¹H
NMR δ: 5.9 (s, 1H), 7.28 (d, J = 8.8, 1H), 7.46 (d, J = 8.5, 2H),
7
.51 (dd, J = 8.8, 2.4, 1H), 7.6 (d, J = 8.5, 2H), 7.64 (d, J = 2.4,