2786
M. Wang et al.
LETTER
Yamagiwa, M.; Matsunaga, S.; Shibasaki, M. Angew. Chem.
Int. Ed. 2007, 46, 409. (d) Nishikata, T.; Lipshutz, B. H.
Org. Lett. 2009, 11, 2377. (e) Roggen, M.; Carreira, E. M.
J. Am. Chem. Soc. 2011, 132, 11917. (f) Hikawa, H.;
Yokoyama, Y. Org. Biomol. Chem. 2011, 9, 4044.
(g) Hikawa, H.; Yokoyama, Y. J. Org. Chem. 2011, 76,
8433. (h) Wagh, Y. S.; Sawant, D. N.; Dhake, K. P.;
Bhanage, B. M. Catal. Sci. Technol. 2012, 2, 835.
After the mixture was concentrated under reduced pressure,
the residue was purified by flash column chromatography on
silica gel and eluted with EtOAc–PE (1:100 to 1:1) to afford
the desired product 3.
Selected spectral data:
Compound 3aa: 1H NMR (400 MHz, CDCl3): δ = 7.07–
7.31 (m, 15 H), 6.41 (d, J = 16.0 Hz, 1 H), 6.17–6.24 (m, 1
H), 3.53 (s, 4 H), 3.12 (d, J = 5.6 Hz, 2 H). 13C NMR (100
MHz, CDCl3): δ = 138.6, 136.1, 131.4, 127.7, 127.5, 127.2,
126.7, 126.2, 125.8, 125.2, 56.9, 54.7. HRMS (ESI): m/z [M
+ H] calcd for C23H24N: 314.1903; found: 314.1909.
Compound 3ad: 1H NMR (400 MHz, CDCl3): δ = 7.56 (d,
J = 6.8 Hz, 1 H), 7.13–7.42 (m, 11 H), 6.94–6.97 (m, 1 H),
6.80 (d, J = 7.6 Hz, 1 H), 6.52 (d, J = 16.0 Hz, 1 H), 6.29–
6.36 (m, 1 H), 3.76 (s, 3 H), 3.66–3.68 (m, 4 H), 3.25 (d, J =
6.4 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 157.7, 140.0,
137.4, 132.3, 129.9, 128.9, 128.6, 128.3, 127.9, 127.8,
127.4, 126.9, 126.4, 120.6, 110.3, 58.4, 56.3, 55.4, 51.5.
HRMS (ESI): m/z [M + H] calcd for C24H26N: 344.2009;
found: 344.2004.
(5) For palladium-catalyzed amination of allylic alcohol without
additive at high temperature, see: (a) Defieber, C.; Ariger,
M. A.; Moriel, P.; Carreira, E. M. Angew. Chem. Int. Ed.
2007, 46, 3139. (b) Mora, G.; Deschamps, B.; van Zutphen,
S.; Goff, X. F. L.; Ricard, L.; Floch, P. L. Organometallics
2007, 26, 1846. (c) Tao, Y.; Wang, B.; Wang, B.; Qu, L.;
Qu, J. Org. Lett. 2010, 12, 2726. (d) Ghosh, R.; Sarkar, A.
J. Org. Chem. 2011, 76, 8508.
(6) For platinum-catalyzed amination of allylic alcohol without
additive at high temperature, see: (a) Utsunomiya, M.;
Miyamoto, Y.; Ipposhi, J.; Ohshima, T.; Mashima, K. Org.
Lett. 2007, 9, 3371. (b) Ohshima, T.; Miyamoto, Y.; Ipposhi,
J.; Nakahara, Y.; Utsunomiya, M.; Mashima, K. J. Am.
Chem. Soc. 2009, 131, 14317. (c) Das, K.; Shibuya, R.;
Nakahara, Y.; Germain, N.; Ohshima, T.; Mashima, K.
Angew. Chem. Int. Ed. 2012, 51, 150. (d) Ohshima, T.;
Mashima, K. J. Synth. Org. Chem., Jpn. 2012, 70, 1145.
(7) General Procedure for Amination of Allylic Alcohols:
Allylic alcohols 1 (0.4 mmol), Pd(Xantphos)Cl2 (0.02 mmol,
5 mol%), amines 2 (0.6 mmol) and 2-PrOH (1.5 mL) were
added to a 25-mL flame-dried Young-type tube under a
nitrogen atmosphere. The mixture was stirred at r.t. for 12 h.
(8) (a) Tsuji, J.; Takahashi, H.; Morikawa, M. Tetrahedron Lett.
1965, 4387. (b) Trost, B. M.; Fullerton, T. J. J. Am. Chem.
Soc. 1973, 95, 292. (c) Trost, B. M.; Vranken, D. L. V.
Chem. Rev. 1996, 96, 395. (d) Tsuji, J. Transition Metal
Reagents and Catalysts; Wiley: New York, 2000.
(e) Godleski, S. A. In Comprehensive Organic Synthesis;
Vol. 3; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: New
York, 1991, 585.
(9) Xie, Y.; Hu, J.; Wang, Y.; Xia, C.; Huang, H. J. Am. Chem.
Soc. 2012, 134, 20613.
Synlett 2014, 25, 2781–2786
© Georg Thieme Verlag Stuttgart · New York