10.1002/chem.201904987
Chemistry - A European Journal
FULL PAPER
[4]
For very important early works on synthesis of primary anilines through
nucleophilic additions of amide to benzynes generated from aryl halides,
see: a) J. D. Roberts, H. E. Simmons Jr., L. A. Carlsmith, C. W. Vaughan,
J. Am. Chem. Soc. 1953, 75, 3290–3291; b) R. A. Benkeser, R. A.
Hickner, D. I. Hoke, O. H. Thomas, J. Am. Chem. Soc. 1958, 80, 5289–
5394; c) R. Levine, E. R. Biehl, J. Org. Chem. 1975, 40, 1835–1837. For
the recent paper of nucleophilic addition of ammonia to 3-
(trimethylsilyl)benzyne generated from phenol derivative, see: d) T.
Ikawa, T. Nishiyama, T, Shigeta, S. Mohri, S. Morita, S.-i. Takayanagi, Y.
Terauchi, Y. Morikawa, A. Takagi, Y. Ishikawa, S. Fujii, Y. Kita, S. Akai,
Angew. Chem. Int. Ed. 2011, 50, 5674–5677; Angew. Chem. 2011, 123,
5792–5795.
Chem. Commun. 2014, 50, 15059−15062; k) T. Ikawa, S. Masuda, A.
Takagi, S. Akai, Chem. Sci. 2016, 7, 5206–5211.
[9]
When Tf2O or PhNTf2 was used instead of NfF, the one-pot benzyne
generation/amination reaction of 2a with KHMDS produced neither 3a
nor triflate 4a’. Similar benzyne generation/amination reactions of 3,5-
dimethoxy-1-halobezenes with KHMDS did not produce 3a (for details of
these results, see Supporting Information). These results indicate that
the in-situ prepared nonaflate 4a is essential for the direct generation of
benzyne through the KHMDS-mediated elimination of the ortho-proton of
the leaving group.
[10] For or selected papers on (Me3Si)3N, see: a) S. Large, N. Roques, B. R.
Langlois, J. Org. Chem. 2000, 65, 8848–8856; b) H. Taneda, K. Inamoto,
Y. Kondo, Chem. Commun. 2014, 50, 6523–6525; c) B. Gao, Y. Zhao,
M. Hu, C. Ni, J. Hu, Chem. Eur. J. 2014, 20, 7803–7810.
[5]
For selected recent reviews on benzynes, see: a) H. Pellissier, M.
Santelli, Tetrahedron 2003, 59, 701–730; b) H. H. Wenk, M. Winkler, W.
Sander, Angew. Chem. Int. Ed. 2003, 42, 502–528; Angew. Chem. 2003,
115, 518–546; c) R. Sanz, Org. Prep. Proced. Int. 2008, 40, 215–291; d)
T. Kitamura, Aust. J. Chem. 2010, 63, 987–1001; e) P. M. Tadross, B. M.
Stoltz, Chem. Rev. 2012, 112, 3550–3577; f) A. V. Dubrovskiy, N. A.
Markina, R. C. Larock, Org. Biomol. Chem. 2013, 11, 191–218; g) S.
Yoshida, T. Hosoya, Chem. Lett. 2015, 44, 1450–1460; h) J. Shi, Y. Li,
Y. Li, Chem. Soc. Rev. 2017, 46, 1707–1719; i) H. Takikawa, A. Nishii,
T. Sakai, K. Suzuki, K. Chem. Soc. Rev. 2018, 47, 8030–8056; j) T. Roya,
A. T. Biju, Chem. Commun. 2018, 54, 2580–2594.
[11] For selected recent theoretical analyses of the regiochemistry of benzyne
reactions, see: a) J. M. Medina, J. L. Mackey, N. K. Garg, K. N. Houk, J.
Am. Chem. Soc. 2014, 136, 15798–15805. b) G.-Y. J. Im, S. M. Bronner,
A. E. Goetz, R. S. Paton, P. H.-Y.Cheong, K. N. Houk, N, K, Garg, J. Am.
Chem. Soc. 2010, 132, 17933–17944. See also Refs. 8f, 8g, and 8h.
[12] For selected papers on the silylaminations of benzynes, see: a) H.
Yoshida, T. Minabe, J. Ohshita, A. Kunai, Chem. Commun. 2005, 3454–
3456; b) S. Yoshida, Y. Nakamura, K. Uchida, Y. Hazama, T. Hosoya,
Org. Lett. 2016, 18, 6212–6215.
[6]
For selected papers detailing the generation of benzynes from phenol
derivatives, see: a) A. Y. Himeshima, T. Sonoda, H. Kobayashi, Chem.
Lett. 1983, 12, 1211–1214; b) P. P. Wickham, K. H. Hazen, H. Guo, G.
Jones, K. H. Reuter, W. J. Scott, J. Org. Chem. 1991, 56, 2045–2050; c)
T. Matsumoto, T. Hosoya, M. Katsuki, K. Suzuki, Tetrahedron Lett. 1991,
32, 6735–6736; d) D. Peña, A. Cobas, D. Pérez, A. Guitián, Synthesis
2002, 1454–1458; e) I. Sapountzis, W. Lin, M. Fischer, P. Knochel,
Angew. Chem. Int. Ed. 2004, 43, 4364–4366; Angew. Chem. 2004, 116,
4464–4466; f) S. M. Bronner, N. K. Garg, J. Org. Chem. 2009, 74, 8842–
8843; g) T. Ikawa, T. Nishiyama, T. Nosaki, A. Takagi, S. Akai, Org. Lett.
2011, 13, 1730–1733; h) S. Kovács, Á. I. Csincsi, T. Zs. Nagy, S. Boros,
G. Timári, Z. Novák, Org. Lett. 2012, 14, 2022–2025; i) Y, Sumida, T.
Kato, T. Hosoya, Org. Lett. 2013, 15, 2806–2809; j) J.-A. García-López,
M. F. Greaney, Org. Lett. 2014, 16, 2338–2341; k) B. Michel, M. F.
Greaney, Org. Lett. 2014, 16, 2684–2687; l) S. Yoshida, K. Uchida, T.
Hosoya, Chem. Lett. 2015, 44, 691–693; m) T. Ikawa, R. Yamamoto, A.
Takagi, T. Ito, K. Shimizu, M. Goto, Y. Hamashima, S. Akai, Adv. Synth.
Catal. 2015, 357, 2287–2300; n) Q. Chen, H. Yu, Z. Xu, L. Lin, X. Jiang,
R. Wang, J. Org. Chem. 2015, 80, 6890–6896; o) Y. Sumida, T. Sumida,
D. Hashizume, T. Hosoya, Org. Lett. 2016, 18, 5600–5603; p) T. Ikawa,
S. Masuda, H. Nakajima, S. Akai, J. Org. Chem. 2017, 82, 4242–4253;
q) M. Mesgar, J. Nguyen-Le, O. Daugulis, J. Am. Chem. Soc. 2018, 140,
13703–13710; r) T. Ikawa, J.-K. Sun, A. Takagi, S. Akai, submitted for
publication.
[13] Based on our experiments into the stability of 2-(trimethylsilyl)aniline 5a
under acidic conditions (1.0 N HCl/aq. THF, room temperature) and the
effects of an acidic workup (for details, see Supporting Information), we
concluded that anilines 3 were not obtained by protodesilylation during
the acidic work-up.
[14] For selected recent examples involving 2,3-pyridynes, see: a) Y. Fang,
R. C. Larock, Tetrahedron 2012, 68 2819–2826; b) N. Saito, K.-i.
Nakamura, S. Shibano, S. Ide, M. Minami, Y. Sato, Org. Lett. 2013, 15,
386–389.
[15] Additional details regarding the substrate scope and limitations are
shown in Supporting Information.
[16] Nonaflate 4a was stable under the conditions of the acidic work-up using
1 N HCl; further details can be found in Supporting Information.
[17] A similar high stability was obtained for the aryl nonaflate than for the
corresponding triflate under alkaline hydrolysis using NaOH has been
previously reported.[6g,7]
[18] For previously reported direct transformation of phenols to anilines, see:
a) M. Mizuno, M. Yamano, Org. Lett. 2005, 7, 3629–3631; b) Y.-S. B. Xie,
V. D. Vijaykumar, K. Jang, H.-H. Shin, H. Zuo, D.-S. Shin, Tetrahedron
Lett. 2013, 54, 5151–51545: c) H. Zeng, Z. Qiu, A. Domínguez-Huerta,
Z. Hearne, Z. Chen, C.-J. Li, ACS Catal. 2017, 7, 510–519; d) Z. Qiu, L.
Lv, J. Li, C.-C. Lia, C.-J. Li, Chem. Sci. 2019, 10, 4775–4781.
[19] Y.-L. Li, J. Li, S.-N. Yu, J.-B. Wang, Y.-M. Yu, J. Deng, Tetrahedron 2015,
71, 8271–8277.
[7]
[8]
For recent reviews on the use of NfF, see: a) H. Vorbrüggen, Synthesis
2008, 1165–1174; b) J. Högermeier, H.-U. Reissig, Adv. Synth. Catal.
2009, 351, 2747–2763.
[20] Y.-L. Sim, A. Ariffin, M. N. Khan, J. Org. Chem. 2007, 72, 2392–2401.
[21] Z. Jiang, N. Liu, G. Dong, Y. Jiang, Y. Liu, X. He, Y. Huang, S. He, Chen,
W. Z. Li, J. Yao, Z. Miao, W. Zhang, Bioorg. Med. Chem. 2014, 24, 4090–
4094.
For selected papers on regioselective benzyne reactions, see: a) T.
Matsumoto, T. Sohma, S. Hatazaki, K. Suzuki, Synlett, 1993, 843−846;
b) H. Yoshida, E. Shirakawa, Y. Honda, T. Hiyama, Angew. Chem. Int.
Ed. 2002, 41, 3247–3249; Angew. Chem. 2002, 114, 3381–3383. c) Z.
Liu, R. C. Larock, J. Am. Chem. Soc. 2005, 127, 13112–13113; d) P. M.
Tadross, C. D. Gilmore, P. Bugga, S. C. Virgil, B. M. Stoltz, Org. Lett.
2010, 12, 1224−1227; e) A. Takagi, T. Ikawa, K. Saito, S. Masuda, T. Ito,
S. Akai, Org. Biomol. Chem. 2013, 11, 8145–8150; f) T. Ikawa, A. Takagi,
M. Goto, Y. Aoyama, Y. Ishikawa, Y. Itoh, S. Fujii, H. Tokiwa, S. Akai, J.
Org. Chem. 2013, 78, 2965–2983; g) A. Takagi, T. Ikawa, Y. Kurita, K.
Saito, K. Azechi, M. Egi, Y. Itoh, H. Tokiwa, Y. Kita, S. Akai, Tetrahedron
2013, 69, 4338–4352; h) T. Ikawa, H. Urata, Y. Fukumoto, Y. Sumii, T.
Nishiyama, S. Akai, Chem. Eur. J. 2014, 20, 16228–16232; i) T. Ikawa,
S. Masuda, T. Nishiyama, A. Takagi, S. Akai, Aust. J. Chem. 2014, 67,
475–480; j) S. Yoshida, K. Uchida, K. Igawa, K. Tomooka, T. Hosoya,
[22] A. B. Durr, G. Yin, I. Kalvet, F. Napoly, F. Schoenebeck, Chem. Sci. 2016,
7, 1076–1081.
[23] J. T. Joseph, A. M. Sajith, R. C. Ningegowda, S. Shashikanth, Adv. Synth.
Catal. 2017, 359, 419–425.
[24] N. Murai, M. Miyano, M. Yonaga, K. Tanaka, Org. Lett. 2012, 14, 2818–
2821.
[25] W. C. Still, M. Kahn, A. Mitra, J. Org. Chem. 1978, 43, 2923–2925.
[26] Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel,
G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone,
B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P.
Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery,
Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N.
This article is protected by copyright. All rights reserved.