Organic Letters
Letter
(11) Jeso, V.; Iqbal, S.; Hernandez, P.; Cameron, M. D.; Park, H. J.;
LoGrasso, P. V.; Micalizio, G. C. Angew. Chem., Int. Ed. 2013, 52, 4800.
(12) Selected C−C bond forming processes where benzoquinone is the
electrophile: (a) Yang, W.; Wang, J.; Wei, Z.; Zhang, Q.; Xu, X. J. Org.
Chem. 2016, 81, 1675. (b) Walker, S. E.; Jordan-Hore, J. A.; Johnson, D.
G.; Macgregor, S. A.; Lee, A. L. Angew. Chem., Int. Ed. 2014, 53, 13876.
(c) Honraedt, A.; Le Callonnec, F.; Le Grognec, E.; Fernandez, V.;
Felpin, F.-X. J. Org. Chem. 2013, 78, 4604. (d) Zhou, T.; Li, L.; Li, B.;
Song, H.; Wang, B. Org. Lett. 2015, 17, 4204. (e) Fujiwara, Y.; Domingo,
V.; Seiple, I. B.; Gianatassio, R.; Del Bel, M. D.; Baran, P. S. J. Am. Chem.
Soc. 2011, 133, 3292. For a radical based method, see: (f) Shaaban, S.;
Jolit, A.; Petkova, D.; Maulide, N. Chem. Commun. 2015, 51, 13902.
(13) Selected studies: (a) Atkinson, R. C.; de la Mare, P. B. D.; Larsen,
D. S. J. Chem. Soc., Perkin Trans. 2 1983, 2, 271. (b) Bansal, V.; Kanodia,
S.; Thapliyal, P. C.; Khanna, R. N. Synth. Commun. 1996, 26, 887.
(c) Kamigata, N.; Satoh, T.; Yoshida, M. Bull. Chem. Soc. Jpn. 1988, 61,
449.
of particular interest, as it demonstrates the power of catalytic C−
H metalation in the design of umpoled strategies.29
ASSOCIATED CONTENT
* Supporting Information
■
S
TheSupportingInformationisavailablefreeofchargeontheACS
Experimental procedures; characterization data and copies
of NMR spectra for all the new compounds; structural
assignments of all compounds were based on detailed
NMR analysis (DEPT, COSY, HSQC, HMBC) (PDF)
(14) Dohi, T.; Nakae, T.; Takenaga, N.; Uchiyama, T.; Fukushima, K.;
Fujioka, H.; Kita, Y. Synthesis 2012, 44, 1183.
(15) Ali, M. H.; Welker, A.; York, C. Synthesis 2015, 47, 3207.
(16) Okada, Y.; Yokozawa, M.; Akiba, M.; Oishi, K.; O-kawa, K.;
Akeboshi, T.; Kawamura, Y.; Inokuma, S.; Nakamura, Y.; Nishimura, J.
Org. Biomol. Chem. 2003, 1, 2506.
AUTHOR INFORMATION
Corresponding Authors
■
Notes
(17) Kvalnes, D. E. J. Am. Chem. Soc. 1934, 56, 667.
(18)Jardim, G. A. M.;daSilvaJunior, E. N.;Bower, J. F. Chem. Sci. 2016,
́
The authors declare no competing financial interest.
7, 3780.
(19) [RhCptCl2]2: (a) Dias, E. L.; Grubbs, R. H. Organometallics 1998,
17, 2758. (b) Hyster, T. K.; Rovis, T. Chem. Commun. 2011, 47, 11846.
(c) Hyster, T. K.; Dalton, D. M.; Rovis, T. Chem. Sci. 2015, 6, 254.
ACKNOWLEDGMENTS
■
G.A.M.J. thankstheCNPqSciencewithoutBordersprogramfora
scholarship. We thank the X-ray crystallography service at the
School of Chemistry, University of Bristol, for analysis of the
products describedhere. J.F.B. isindebtedtotheRoyalSocietyfor
the provision of a University Research Fellowship. E.N.S.J. thanks
the Royal Society of Chemistry for a JWT Jones Travelling
Fellowship, and CAPES, FAPEMIG and CNPq for research
support.
(d) Piou, T.; Rovis, T. Nature 2015, 527, 86. [RhCp*CF Cl2]2: (e) Neely,
3
J. M.; Rovis, T. J. Am. Chem. Soc. 2014, 136, 2735. (f) Romanov-
Michailidis, F.; Sedillo, K. F.; Neely, J. M.; Rovis, T. J. Am. Chem. Soc.
2015, 137, 8892. [RhCpi‑PrCl2]2: (g) Piou, T.; Rovis, T. J. Am. Chem. Soc.
2014, 136, 11292.
(20) Conventional methods require highly activated systems or
proceed via ipso-iodination of silyl-benzoquinones. Representative
examples: (a) Kitson, R. R. A.; Chang, C.-H.; Xiong, R.; Williams, H.
E. L.; Davis, A. L.; Lewis, W.; Dehn, D. L.; Siegel, D.; Roe, S. M.;
Prodromou, C.; Ross, D.; Moody, C. J. Nat. Chem. 2013, 5, 307.
(b) Chan, K. S.; Mak, C. C. Tetrahedron 1994, 50, 2003.
REFERENCES
■
(1) Monks, T. J.; Hanzlik, P.; Cohen, G. M.; Ross, D.; Graham, D. G.
Toxicol. Appl. Pharmacol. 1992, 112, 2.
(2) Turunen, M.; Olsson, J.; Dallner, G. Biochim. Biophys. Acta,
(21) (a) Jamier, V.; Ba, L. A.; Jacob, C. Chem. - Eur. J. 2010, 16, 10920.
(b) Shaaban, S.; Diestel, R.; Hinkelmann, B.; Muthukumar, Y.; Verma, R.
P.; Sasse, F.; Jacob, C. Eur. J. Med. Chem. 2012, 58, 192.
Biomembr. 2004, 1660, 171.
(22) Vieira, A. A.; Brandao, I. R.; Valenca
Cavalcanti, B. C.; Pessoa, C.; Carneiro, T. R.; Braga, A. L.; da Silva Junior,
E. N. Eur. J. Med. Chem. 2015, 101, 254.
̧
, W. O.; de Simone, C. A.;
̃
(3) (a) O’Brien, P. J. Chem.-Biol. Interact. 1991, 80, 1. (b) Bolton, J. L.;
Trush, M.; Penning, T.; Dryhurst, G.; Monks, T. J. Chem. Res. Toxicol.
2000, 13, 135. (c) Monks, T. J.; Jones, D. C. Curr. Drug Metab. 2002, 3,
425. Reviews that encompass this issue: (d) Hillard, E. A.; de Abreu, F.
C.; Ferreira, D. C. M.; Jaouen, G.; Goulart, M. O. F.; Amatore, C. Chem.
Commun. 2008, 2612. (e) de Paiva, Y. G.; Ferreira, F. R.; Silva, T. L.;
Labbe, E.; Buriez, O.; Amatore, C.; Goulart, M. O. F. Curr. Top. Med.
́
Chem. 2015, 15, 136.
(4) Prochazka, E.; Escher, B. I.; Plewa, M. J.; Leusch, F. D. L. Chem. Res.
Toxicol. 2015, 28, 2059.
(5) Mout, R.; Xu, Z. D.; Wolf, A. K. H.; Davisson, V. J.; Jarori, G. K.
Malar. J. 2012, 11, 54.
́
(23) Rh-catalyzed C−H selenation of arenes: Yu, S.; Wan, B.; Li, X. Org.
Lett. 2015, 17, 58.
(24) Sakakibara, M.; Watanabe, Y.; Toru, T.; Ueno, Y. J. Chem. Soc.,
Perkin Trans. 1 1991, 1231.
(25)(a)Colacot, T. J.;Shea, H. A. Org.Lett. 2004,6,3731. (b)Mee,S.P.
H.; Lee, V.; Baldwin, J. E. Angew. Chem., Int. Ed. 2004, 43, 1132.
(26) Schroder, N.; Wencel-Delord, J.; Glorius, F. J. Am. Chem. Soc.
̈
2012, 134, 8298.
(27) Under the conditions shown in Table 1, entry 10, replacement of
CuSO4 with other Cu(II) salts, such as Cu(OAc)2 or Cu(OTf)2,
provided inferior results (Cu(OAc)2: 10% yield of 2a, Cu(OTf)2:
complex mixture of products).
(28) Because the reactions described here are conducted in sealed tubes
we have been unable to undertake accurate side-by-side rate measure-
ments for the iodination of 1a and deuterio-1a. An intramolecular
competition experiment between 1a and deuterio-1a is given in the
Supporting Information. For a discussion on the interpretation of KIE
measurements, see: Hartwig, J. F.; Simmons, E. M. Angew. Chem., Int. Ed.
2012, 51, 3066.
(6) Tasdemir, D.; Brun, R.; Yardley, V.; Franzblau, S. G.; Ruedi, P.
Chem. Biodiversity 2006, 3, 1230.
̈
(7) As reported by Fieser and Chamberlin, the isolation of embelin was
described in the doctoral dissertation of Earl M. Chamberlin, May 6,
1940. Fieser, L. F.; Chamberlin, E. M. J. Am. Chem. Soc. 1948, 70, 71.
(8) Joy, B.; Kumar, S. N.; Soumya, M. S.; Radhika, A. R.; Vibin, M.;
Abraham, A. Phytomedicine 2014, 21, 1292.
(9) Cavalli, A.; Bolognesi, M. L.; Capsoni, S.; Andrisano, V.; Bartolini,
M.; Margotti, E.; Cattaneo, A.; Recanatini, M.; Melchiorre, C. Angew.
Chem., Int. Ed. 2007, 46, 3689. For a recent review related to memoquin
and multitarget drugs, see: Prati, F.; Uliassi, E.; Bolognesi, M. L.
MedChemComm 2014, 5, 853.
(29) Attempts to promote reactions with other electrophiles, such as
selectfluor, NCS, and N-(phenylthio)phthalimide, have so far been
unsuccessful. A full study will be reported in due course.
(10) Smith, D. F.; Whitesell, L.; Nair, S. C.; Chen, S.; Prapapanich, V.;
Rimerman, R. A. Mol. Cell. Biol. 1995, 15, 6804.
D
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