Journal of the American Chemical Society
ground state? Natural bond orbital (NBO) analyses of the
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9 Murphy, K. E.; Bocanegra, J. L.; Liu, X.; Chau, H.-Y. K.; Lee, P.
carbon atoms on the aromatic rings show more positive
charge character on the trifluoromethylated ring regardless
of the presence (6) or absence (14) of the hydroxyl group
(Table S3). Thus, the HO—arene activation must be more
influential during the formation of the σ-complex.
C.; Li, J.; Schneebeli, S. T. Nature Commun. 2017, 8, 14840.
10 Holl, M. G.; Struble, M. D.; Singal, P.; Siegler, M. A.; Lectka, T.
Angew. Chem. Int. Ed. 2016, 55, 8266-8269.
11 Struble, M. D.; Holl, M. G.; Coombs, G.; Siegler, M.; Lectka, T. J.
Org. Chem. 2015, 80, 4803−4807.
12 Meyer, E. A.; Castellano, R. K.; Diederich, F. Angew. Chem. Int.
Ed. 2003, 42, 1210-1250.
13 Ji, X.; Zhang, P.; Armstrong, R. N.; Gilliland, G. L. Biochemistry
1992, 31, 10169-10184.
Figure 2.
Optimized structure of 6A, the σ-complex
intermediate for endo-bromination of 6, at ωB97XD/6-
311+G**.
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Br
H
14 Xiao, G.; Liu, S.; Ji, X.; Johnson, W. W.; Chen, J.; Parons, J. F.;
Stevens, W. J.; Gilliland, G. L.; Armstrong, R. N. Biochemistry 1996,
35, 4753-4765.
H
Cl
H
Cl
H
d(C1-O)
d(C2-O)
=
=
1.47 A
1.57 A
O
H
CF3
C1
C2
15 Sulpizi, M.; Carloni, P. J. Phys. Chem. B. 2000, 104, 10087-10091.
16 Kryger, G.; Silman, I.; Sussman, J. L. Structure 1999, 7, 297-307.
17 Kryger, G.; Silman, I.; Sussman, J. L. J. Phisiol. Paris 1992, 92,
191-194.
18 Banerjee, P.; Chakraborty, T. J. Phys. Chem. A 2014, 118, 7074−
7084.
O
O
6A
O
In conclusion, we demonstrated that the HO—aryl
interaction dramatically increases an aromatic ring's
reactivity with electrophiles such that this phenomenon
may override the influence of deactivating substituents. In
19 Malenov, D. P.; Janjic, G. V.; Veljkovic, D. Z.; Zaric, S. D. Comp.
Theor. Chem. 2013, 1018, 59−65.
20 Saggu, M.; Levinson, N. M.; Boxer, S. G. J. Am. Chem. Soc. 2011,
133, 17414−17419.
particular, preferential EAS on
a
trifluoromethyl-
21
Mohan, N.; Vijayalakshmi, K. P.; Koga, N.; Suresh, C. H. J.
substituted ring over a comparable unsubstituted aromatic
ring is a testament to the strength of this interaction. Not
only does this expand the selectivity "rules" of EAS in
chemical synthesis based on substituent effects, but it
should also draw attention to interactions in, for instance,
enzyme active sites where forced HO—arene interactions
are plausible.
Comput. Chem. 2010, 31, 2874−2882.
22 Toth, G.; Bowers, S. G.; Truong, A. P.; Probst, G. Curr. Pharm.
Des. 2007, 13, 3476−3493.
23 Motherwell, W. B.; Moïse, J.; Aliev, A. E.; Nič, M.; Coles, S. J.;
Horton, P. N.; Hursthouse, M. B.; Chessari, G.; Hunter, C. A.; Vinger,
J. G. Angew. Chem. Int. Ed. 2007, 46, 7823 –7826.
24 Aliev, A. E.; Arendorf, J. R. T.; Pavlakos, I.; Moreno, R. B.; Porter,
M. J.; Rzepa, H. S.; Motherwell, W. B. Angew. Chem. Int. Ed. 2015,
54, 551-555.
25 Paruch, K.; Vyklický, L.; Wang, D. Z.; Katz, T. J.; Incarvito, C.;
Zakharov, L.; Rheingold, A. L. J. Org. Chem. 2003, 68, 8539-8544.
Supporting Information. General experimental procedures
and characterization data can be found therein. CCDC
1545393, 1547865, and 1547866 contain the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from the Cambridge Crystallographic
Data Centre.
26
Hong, J.; Yang, G.; Duan, C.; Guo, Z.; Zhu, L. Inorg. Chem.
Commun. 2005, 8, 988-991.
27 Ferguson, G.; Gallagher, J. F. Acta Cryst. 1994, 50, 70-73.
28 Carr, G. E.; Chambers, R. D.; Holmes, T. F. J. Chem. Soc. Perkin
Trans. 1 1988, 1, 921-926.
AUTHOR INFORMATION
29 Gustafson, J. L.; Lim, D.; Miller, S. J. Science 2010, 328, 1251-
1255.
30 Pathak, T. P.; Miller, S. J. J. Am. Chem. Soc. 2012, 134, 6120-6123.
31 Rosenthal, J.; Schuster, D. I. J. Chem. Educ. 2003, 80, 679-690.
The authors declare no competing financial interests.
Correspondence and requests for materials should be
addressed to lectka@jhu.edu.
32 Roberts, J. D.; Sanford, J. K.; Sixma, F. L. J.; Cerfontain, H.; Zagt,
ACKNOWLEDGMENTS
T.L. thanks the NSF (CHE 1465131) for financial support.
R. J. Am. Chem. Soc. 1954, 76, 4525-4534.
33 Nieves-Quinones, Y.; Singleton, D. J. Am. Chem. Soc. 2016, 138,
15167-15176.
REFERENCES
34 Reich, H. J.; Cram, D. J. J. Am. Chem. Soc. 1969, 91, 3505-3516.
35 Bondarenko, L.; Kampf, J. W.; Lahann, J. Eur. J. Org. Chem. 2006,
1 Ferguson, L. N. Chem. Rev. 1952, 50, 47-67.
2 Galabov, B.; Nalbantova, D.; Schleyer, P. v. R.; Schaefer III, H. F.
Acc. Chem. Res. 2016, 49, 1191-1199.
24, 5499-5504.
36 Carey, F. A. Organic Chemistry, 4th ed.; McGraw Hill: New York,
2000.
37 The O-methylated derivatives of 1 and 6 brominate preferentially
on the top ring, consistent with activation by the O-atom. See SI for
details.
3 Gilow, H. J. Chem. Ed. 1977, 54, 450-452.
4 Pollit, R. J.; Saunders, B. C. J. Chem. Soc. 1964, 1132-1135.
5 Ueda, H.; Sakabe, N.; Tanaka, J.; Furusaki, A. Bull. Chem. Soc. Jpn.
1968, 41, 2866-2871.
38 Diels, O.; Alder, K. Liebigs Ann. Chem. 1931, 490, 236−242.
39 McMurry, J. E.; Lectka, T. Acc. Chem. Res.
40 Bader, R. F. W. Acc. Chem. Res. 1985, 18, 9-15.
6
1992, 25, 47-53.
Chiavarino, B.; Crestoni, M. E.; Fornarini, S.; Lanucara, F.;
Lemaire, J.; Maître, P. Angew. Chem. Int. Ed. 2007, 46, 1995-1998.
7 Glukhovtsev, M. N.; Bach, R. D.; Laiter, S. J. Org. Chem. 1997, 62,
4036-4046.
8 Giroldo, T.; Xavier, L. A.; Riveros, J. M. Angew. Chem. Int. Ed.
2004, 43, 3588-3590.
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