DOI: 10.1039/C5CC01519G
ChemComm
COMMUNICATION
Journal Name
MINECO, co-financed by the European Regional Development 11 (a) J. Verrax, R. Beck, N. Dejeans, C. Glorieux, B. Sid, R. C. Pedrosa,
Fund (ERDF), CTQ2011-28417-C02-01, and CTQ2011-22653.
G.S.-D. thanks EU Social Fund (FSE) and ACIISI for a pre-
doctoral fellowship.
J. Benites, D. Vásquez, J. A. Valderrama and P. B. Calderon,
Anticancer Agents Med. Chem., 2011, 11, 213-221; (b) R. Pethig, P.
R. C. Gascoyne, J. A. Mclaughlin and A. Szent-Gyorgyi, Proc. Natl.
Acad. Sci., 1983, 80, 129-132; (c) J. Verrax, J. Cadrobbi, M. Delvaux,
J. M. Jamison, J. Gilloteaux, J. L. Summers, H. S. Taper and P. B.
Calderon, Eur. J. Med. Chem., 2003, 38, 451-457; (d) R. Beck, J.
Verrax, N. Dejeans, H. Taper and P. B. Calderon, Int. J. Tox., 2009,
28, 33-42.
Dedicated in memoriam to Prof. Tsutomu Katsuki
Notes and references
a
Departamento de Química Orgánica, Instituto Universitario de Bio-
Orgánica “Antonio González” (IUBO), Centro de Investigaciones
Biomédicas de Canarias (CIBICAN), Universidad de La Laguna. Avda. 12 Q. Chen, M. G. Espey, A. Y. Sun, J.-H. Lee, M. C. Krishna, E. Shacter,
Astrofísico Fco. Sánchez 2, Apdo. Correos 456, 38200 – La Laguna, S/C.
P. L. Choyke, C. Pooput, K. L. Kirk, G. R. Buettner and M. Levine,
de Tenerife (Spain).
Proc. Natl. Acad. Sci., 2007, 104, 8749-8754.
b
Instituto de Productos Naturales y Agrobiología, CSIC Avda. Astrofísico 13 (a) Z. He and T. F. Jamison, Angew. Chem. Int. Ed., 2014, 53, 3353-
Fco. Sánchez, 3, 38206 La Laguna, S/C. de Tenerife (Spain).
Electronic Supplementary Information (ESI) available: Full experimental
3357; (b) Y.-Q. Zou, J.-R. Chen, X.-P. Liu, L.-Q. Lu, R. L. Davis, K.
A. Jørgensen and W.-J. Xiao, Angew. Chem. Int. Ed., 2012, 51, 784-
788; (c) S. P. Pitre, C. D. McTiernan, H. Ismaili and J. C. Scaiano, J.
Am. Chem. Soc., 2013, 135, 13286−13289; (d) C. Zhu, R. Wang and J.
R. Falck, Org. Lett., 2012, 14, 3494-3497; (e) Y. Zhong, L. Yuan, Z.
†
details, spectroscopic data and copies of NMR spectra. See
DOI: 10.1039/c000000x/
1
(a) Modern Oxidation Methods (Ed.: J. E. Bäckvall), VCH-Wiley,
Weinheim, 2004; (b) R. A. Sheldon, I. W. C. E. Arends, G.-J. Ten
Brink, A. Dijksman, Acc. Chem. Res., 2002, 35, 774-781; (c) R.
Noyori, M. Aoki, K. Sato, Chem. Commun., 2003, 1977-1983.
(a) J. Piera and J.-E- Bäckvall, Angew. Chem. Int. Ed., 2008, 47, 3506-
Huang, W. Gu, Y. Shao and W. Han, RSC Adv., 2014, 4, 33164-33167;
(f) H. Jiang, L. Lykke, S. U. Pedersen, W.-J. Xiao and K. A. Jørgensen,
Chem. Commun., 2012, 48, 7203-7205; (g) W. Ding, J.-R. Chen, Y.-
Q. Zou, S.-W. Duan, L.- Q. Lu and W.-J. Xiao, Org. Chem. Front.,
2
3
4
2014, 1, 151-154; (h) P. Kaewmati, E. Somsook, R. N. Dhital and H.
3
2
523, and references therein; (b) A. Berkessel, Adv. Inorg. Chem.,
006, 58, 1-28.
Sakurai, Tetrahedron Lett., 2012, 53, 6104-6106.
14 J. N. Bull, C. W. West and J. R. Verlet, Chem. Sci., 2015,
1589.
6
, 1578-
(a) B. F. Minaev, Int. J. Quantum. Chem., 1980, 17, 367-374; (b) A. L.
Buchchenko and V. L. Berdinsky, J. Phys. Chem., 1996, 100, 18292- 15 E. J. Nanni, Jr., M. D. Stallings and D. T. Sawyer, J. Am. Chem. Soc.,
8299. 1980, 102, 4481-4485.
Paramagnetic metals can use the exchange interaction between the 16 G. B. Payne, P. H. Deming and P. H. Williams, J. Org. Chem., 1961,
unpaired spin of the metal and the oxygen species for an effective 26, 659-663.
intersystem crossing, which allows the triplet to singlet spin flip. See: 17 Reactions under pure O
1
2
led to similar yields. We chose open flask
R. Prabhakar, P. E. M. Siegbahn, B. F. Minaev and H. Ågren, J. Phys
Chem. B, 2004, 108, 13882-13892.
reactions because they are much more sustainable and affordable.
18 (a) H. Yao and D. E. Richardson, J. Am. Chem. Soc., 2000, 122, 3220-
3221; (b) D. E. Richardson, H. Yao, K. M. Frank and D. A. Bennett,
J. Am. Chem. Soc., 2000, 122, 1729-1739; (c) B. Balagam and D. E.
Richardson, Inorg. Chem., 2008, 47, 1173-1178.
5
6
P. Anastas and N. Eghbali, Chem. Soc. Rev., 2010, 39, 301-312.
(a) H. Kawai, S. Okusu, Z. Yuan, E. Tokunaga, A. Yamano, M. Shiro
and N. Shibata, Angew. Chem. Int. Ed., 2013, 52, 2221 –2225; (b) Y.
Imada, H. Iida, S. Ono and S.-I. Murahashi, J. Am. Chem. Soc., 2003, 19 Initial attempts to oxidize alkenyl boronic acids were unsuccessful.
25, 2868-2869; (c) F. Hollmann, A. Taglieber, F. Schulz and M. T. 20 We have chosen known transition metal free reactions in order to
1
Reetz, Angew. Chem. Int. Ed., 2007, 46, 2903-2906; (d) S. Chen and
F. W. Foss Jr., Org. Lett., 2012, 14, 5150-5153; (e) R. Liu, X. Liang,
assure that metals have no influence in the generation of hydrogen
peroxide or other reactive oxygen species.
C. Dong and X. Hu, J. Am. Chem. Soc., 2004, 126, 4112-4113; (f) R. 21 W.Zhuang, M. Marigo and K. A. Jørgensen, Org. Biomol. Chem.,
Mu, Z. Liu, Z. Yang, Z. Liu, L. Wu and Z.-L. Liu, Adv. Synth. Catal., 2005, , 3883-3885.
005, 347, 1333-1336.
Industrial production of H
3
2
22 Promising results with chiral prolinol derivatives will be reported
elsewhere.
7
2 2
O relies almost exclusively in the
anthraquinone oxidation method, which is catalyzed by transition 23 P. Wright and J. Abbot, Int. J. Chem. Kinet., 1993, 25, 901-911.
metals. See: J. M. Campos-Martin, G. Blanco-Brieva, J. L. G. Fierro, 24 E. V. Bakhmutova-Albert, H. Yao, D. E. Denevan and D. E.
Angew. Chem. Int. Ed., 2006, 45, 6962-6984.
Richardson, Inorg. Chem., 2010, 49, 11287-11296.
8
9
Y. Song, G. Buettner, Free Radic. Biol. Med., 2010, 49, 919-962.
Usually ascorbate has only been used to reduce some metals, mainly
Cu(II) to Cu(I), like in the CuCAAC “click“ reaction. For other uses
25 (a) W. C. Ellis, C. T. Tran, R. Roy, M. Rusten, A. Fischer, A. D.
Ryabov, B. Blumberg and T. J. Collins, J. Am. Chem. Soc., 2010, 132
9774-9781. (b) B. M. Smith, Chem. Soc. Rev., 2008, 37, 470-478.
,
in synthesis, see: (a) F. P. Crisóstomo, T. Martín and R. Carrillo 26 J. Marsh, R. M. Dahlgren, C. Clarke, J. Stonehouse and C. Nunn, J.
Angew. Chem. Int. Ed., 2014, 53, 2181-2185; (b) D. L. Browne, I. R.
Baxendale and S. V. Ley, Tetrahedron, 2011, 67, 10296-10303.
0 V. Roginsky, T. Barsukova and H. B. Stegmann, Chem. Biol. Interact.,
Cosmet. Sci., 2009, 60, 205-215.
27 S. Sánchez, L. Soler and J. Katuri, Angew. Chem. Int. Ed., 2015, 54
1414-1444, and references therein.
,
1
1
999, 121, 177–197.
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012