G
V. Ajdačić et al.
Paper
Synthesis
1H NMR (500 MHz, CDCl3): δ = 7.74–7.65 (m, 5 H), 7.43 (s, 1 H), 7.32–
7.29 (m, 4 H), 7.29–7.24 (m, 2 H), 7.03–6.97 (m, 2 H).
13C NMR (125 MHz, CDCl3): δ = 162.1 (d, J = 245.5 Hz), 140.4, 140.1,
138.4, 138.2, 133.4, 132.8, 132.0 (d, J = 2.7 Hz), 130.6 (d, J = 8.1 Hz),
129.1, 128.7, 128.2, 128.1, 125.7, 118.8, 115.5 (d, J = 21.6 Hz), 110.7.
GC–MS: m/z = 355.1 [M]+.
HRMS (ESI): m/z [M + H]+ calcd for C23H15FNS: 356.09037; found:
(3) (a) Tsuji, J.; Ohno, K. Tetrahedron Lett. 1965, 6, 3969. (b) Ohno,
K.; Tsuji, J. J. Am. Chem. Soc. 1968, 90, 99. (c) Tsuji, J.; Ohno, K.
Synthesis 1969, 157. (d) Walborsky, H. M.; Allen, L. E. J. Am.
Chem. Soc. 1971, 93, 5465. (e) Ziegler, F. E.; Belema, M. J. Org.
Chem. 1997, 62, 1083. (f) Zeng, C.-M.; Han, M.; Covey, D. F. J. Org.
Chem. 2000, 65, 2264. (g) Kato, T.; Hoshikawa, M.; Yaguchi, Y.;
Izumi, K.; Uotsu, Y.; Sakai, K. Tetrahedron 2002, 58, 9213.
(h) Harmata, M.; Wacharasindhu, S. Org. Lett. 2005, 7, 2563.
(i) Malerich, J. P.; Maimone, T. J.; Elliott, G. I.; Trauner, D. J. Am.
Chem. Soc. 2005, 127, 6276. (j) Zhang, H.; Padwa, A. Tetrahedron
Lett. 2006, 47, 3905. (k) Padwa, A.; Zhang, H. J. Org. Chem. 2007,
72, 2570.
356.09103.
Computational Details
The calculations using the restricted Kohn–Sham formalism have
been performed with the Amsterdam Density Functional (ADF) pro-
gram package, version 2013.01,22 with hybrid exchange-correlation
approximation B3LYP.23 Grimme’s dispersion (D3) correction has
been included.24 Molecular orbitals (MOs) were expanded in an un-
contracted set of Slater-type orbitals (STOs) of triple-ζ quality con-
taining diffuse functions (TZP) and two sets of polarization functions.
Only full-electron basis was employed. An auxiliary set of s, p, d, f, and
g STOs was used to fit the molecular density and to represent the
Coulomb and exchange potentials accurately for each self-consistent
field (SCF) cycle. Since ADF utilizes STOs, all integrals are calculated
numerically, and thus the results may be sensitive to the quality of
the integration grid (Becke grid good was used in all calculations).
The geometries of the intermediate species were optimized with the
QUILD25 program using adapted delocalized coordinates until the
maximum gradient component was less than 10–4 au. Transition state
structures were located using linear transit methodology, and then
further relaxed with the transition state optimization algorithm. Nu-
merical harmonic frequencies were calculated, and in all cases the
nature of the stationary point was confirmed by the presence of ei-
ther zero or one imaginary frequency modes. The imaginary frequen-
cy mode, present in saddle-point transition state structures, was vi-
sualized and confirmed to be a reaction coordinate for the bromine
addition. Intrinsic reaction coordinate (IRC)26 methodology was used
in order to connect the transition states with σ-complex intermediate
structures. In addition, thermochemical properties are derived at P =
1 atm and T = 298.15 K by using the standard statistical-mechanics
relationships for an ideal gas.
(4) (a) Doughty, D. H.; Pignolet, L. H. J. Am. Chem. Soc. 1978, 100,
7083. (b) Boeckman, R. K. Jr.; Zhang, J.; Reeder, M. R. Org. Lett.
2002, 4, 3891. (c) Fristrup, P.; Kreis, M.; Palmelund, A.; Norrby,
P. O.; Madsen, R. J. Am. Chem. Soc. 2008, 130, 5206. (d) Patra, T.;
Manna, S.; Maiti, D. Angew. Chem. Int. Ed. 2011, 50, 12140.
(5) (a) Hawthorne, J. O.; Wilt, M. H. J. Org. Chem. 1960, 25, 2215.
(b) Tsuji, J.; Ohno, K.; Kajimoto, T. Tetrahedron Lett. 1965, 6,
4565. (c) Tsuji, J.; Ohno, K. J. Am. Chem. Soc. 1968, 90, 94.
(d) Wilt, J. W.; Pawlikowski, W. W. J. Org. Chem. 1975, 40, 3641.
(e) Matsubara, S.; Yokota, Y.; Oshima, K. Org. Lett. 2004, 6, 2071.
(6) Modak, A.; Deb, A.; Patra, T.; Rana, S.; Maity, S.; Maiti, D. Chem.
Commun. 2012, 48, 4253.
(7) (a) Shibata, T.; Toshida, N.; Yamasaki, M.; Maekawa, S.; Takagi,
K. Tetrahedron 2005, 61, 9974. (b) Kwong, F. Y.; Lee, H. W.; Lam,
W. H.; Qiu, L.; Chan, A. S. C. Tetrahedron: Asymmetry 2006, 17,
1238. (c) Iwai, T.; Fujihara, T.; Tsuji, Y. Chem. Commun. 2008,
6215.
(8) (a) Domazetis, G.; Tarpey, B.; Dolphin, D.; James, B. R. J. Chem.
Soc., Chem. Commun. 1980, 939. (b) Park, K. H.; Son, S. U.;
Chung, Y. K. Chem. Commun. 2003, 1898.
(9) (a) Ghosh, C. K.; Khan, S. Synthesis 1981, 719. (b) Ghosh, C. K.;
Bandyopadhyay, C.; Tewari, N. J. Org. Chem. 1984, 49, 2812.
(10) Tiwari, B.; Zhang, J.; Chi, Y. R. Angew. Chem. Int. Ed. 2012, 51,
1911.
(11) (a) Tang, R.-J.; Kang, L.; Yang, L. Adv. Synth. Catal. 2015, 357,
2055. (b) Tang, R.-J.; He, Q.; Yang, L. Chem. Commun. 2015, 51,
5925.
(12) Venkateswarlu, V.; Kumar, K. A. A.; Gupta, S.; Singh, D.;
Vishwakarma, R. A.; Sawant, S. D. Org. Biomol. Chem. 2015, 13,
7973.
(13) Malamidou-Xenikaki, E.; Tsanakopoulou, M.; Chatzistefanou,
M.; Hadjipavlou-Litina, D. Tetrahedron 2015, 71, 5650.
(14) Bhosale, S. M.; Momin, A. A.; Kunjir, S.; Rajamohanan, P. R.;
Kusurkar, R. S. Tetrahedron Lett. 2014, 55, 155.
Acknowledgment
This research was financially supported by the Ministry of Education,
Science and Technological Development of Serbia (Grant No. 172008)
and the Serbian Academy of Sciences and Arts.
(15) Lynch, B. J.; Truhlar, D. G. J. Phys. Chem. A 2001, 105, 2936.
(16) (a) Han, Y.; Giroux, A.; Lepine, C.; Laliberte, F.; Huang, Z.;
Perrier, H.; Bayly, C. I.; Young, R. N. Tetrahedron 1999, 55, 11669.
(b) Mortensen, D. S.; Rodriguez, A. L.; Carlson, K. E.; Sun, J.;
Katzenellenbogen, B. S.; Katzenellenbogen, J. A. J. Med. Chem.
2001, 44, 3838. (c) Brendle, J. J.; Outlaw, A.; Kumar, A.; Boykin,
D. W.; Patrick, D. A.; Tidwell, R. R.; Werbovetz, K. A. Antimicrob.
Agents Chemother. 2002, 46, 797. (d) Givens, M. D.; Dykstra, C.
C.; Brock, K. V.; Stringfellow, D. A.; Kumar, A.; Stephens, C. E.;
Goker, H.; Boykin, D. W. Antimicrob. Agents Chemother. 2003, 47,
2223. (e) Chandra, R.; Kung, M.-P.; Kung, H. F. Bioorg. Med.
Chem. Lett. 2006, 16, 1350. (f) Bey, E.; Marchais-Oberwinkler, S.;
Negri, M.; Kruchten, P.; Oster, A.; Klein, T.; Spadaro, A.; Werth,
R.; Frotscher, M.; Birk, B.; Hartmann, R. W. J. Med. Chem. 2009,
52, 6724. (g) Min, J.; Wang, P.; Srinivasan, S.; Nwachukwu, J. C.;
Guo, P.; Huang, M.; Carlson, K. E.; Katzenellenbogen, J. A.;
Nettles, K. W.; Zhou, H.-B. J. Med. Chem. 2013, 56, 3346.
Supporting Information
Supporting information for this article is available online at
S
u
p
p
ortioInfgrmoaitn
S
u
p
p
ortiInfogrmoaitn
References
(1) Ortiz de Montellano, P. R. In Cytochrome P450: Structure, Mecha-
nism, and Biochemistry, 4th ed.; Ortiz de Montellano, P. R., Ed.;
Springer International Publishing: Switzerland, 2015, 154.
(2) (a) Garralda, M. A. Dalton Trans. 2009, 3635. (b) Modak, A.;
Maiti, D. Org. Biomol. Chem. 2016, 14, 21.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H