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D.-C. Bai et al.
Letter
Synlett
tions; VCH: New York, 1989. (c) Najera, C.; Sansano, J. M. Chem.
Rev. 2007, 107, 4584. (d) Ordόñez, M.; Cativiela, C. Tetrahedron:
Asymmetry 2007, 18, 3. (e) Metz, A. E.; Kozlowski, M. C. J. Org.
Chem. 2015, 80, 1.
sealed tube (10 mL) and stirred at r.t. for 30 min. Compound 1
(0.2 mmol), TMSCN (30 μL, 0.2 mmol), and toluene (1.0 mL)
were added to the sealed tube, then the reaction mixture was
stirred at 120 °C immediately. After the reaction time show in
Table 2, the reaction mixture was quenched by sat. Na2CO3 (0.5
mL) and extracted with EtOAc (3 × 10 mL). The organic layer was
combined, dried (anhydrous Na2SO4), filtered, and concentrated
in vacuo to afford a crude oil. Purification by chromatography
on silica gel provided the desired product (eluting with PE–
EtOAc = 10:1)
(3) (a) Huang, J. K.; Haar, C. M.; Nolan, S. P.; Marcone, J. E.; Moloy, K.
G. Organometallics 1999, 18, 297. (b) Zapf, A.; Beller, M. Top.
Catal. 2002, 19, 101. (c) Fleming, F. F.; Yao, L. H.; Ravikumar, P.
C.; Funk, L.; Shook, B. C. J. Med. Chem. 2010, 53, 7902. (d) Jiang,
W.; Liu, H. Chin. J. Org. Chem. 2012, 32, 1643.
(4) (a) Enders, D.; Shilvock, J. P. Chem. Soc. Rev. 2000, 29, 359.
(b) Gröger, H. Chem. Rev. 2003, 103, 2795. (c) Khan, N. H.;
Kureshy, R. I.; Abdi, S. H. R.; Agrawal, S.; Jasra, R. V. Coord. Chem.
Rev. 2008, 252, 593. (d) North, M.; Usanov, D. L.; Young, C. Chem.
Rev. 2008, 108, 5146. (e) Salter, M. M.; Fossey, J. S.; Mori, Y.;
Kobayashi, S. Chem. Rev. 2011, 111, 2626. (f) Wang, J.; Liu, X.;
Feng, X. Chem. Rev. 2011, 111, 6947. (g) Ohkuma, T.; Kurono, N.
Synlett 2012, 23, 1865.
(5) For reviews, see: (a) Trost, B. M.; Van Vranken, D. L. Chem. Rev.
1996, 96, 395. (b) Trost, B. M.; Crawley, M. L. Chem. Rev. 2003,
103, 2921. (c) Lu, Z.; Ma, S. Angew. Chem. Int. Ed. 2008, 47, 258.
(d) Ding, C.-H.; Hou, X.-L. Top. Organomet. Chem. 2011, 36, 247.
For some examples, see: (e) You, S.-L.; Zhu, X.-Z.; Luo, Y.-M.;
Hou, X.-L.; Dai, L.-X. J. Am. Chem. Soc. 2001, 123, 7471. (f) Cheng,
H.-B.; Feng, B.; Chen, L.-Y.; Guo, W.; Yu, X.-Y.; Lu, L.-Q.; Chen, J.-
R.; Xiao, W.-J. Chem. Commun. 2014, 50, 2873. (g) Feng, B.;
Cheng, H.-B.; Chen, J.-R.; Deng, Q.-H.; Lu, L.-Q.; Xiao, W.-J. Chem.
Commun. 2014, 50, 9550. (h) Yang, H.; Zhou, H.; Yin, H.; Xia, C.;
Jiang, G. Synlett 2014, 25, 2149. (i) Baeza, A.; Nájera, C. Synthesis
2014, 46, 25. (j) Alberch, E.; Brook, C.; Asad, S. A.; Shevyrev, M.;
Ulicki, J. S.; Hossain, M. M. Synlett 2015, 26, 388. (k) Chen, T.-G.;
Fang, P.; Hou, X.-L.; Dai, L.-X. Synthesis 2015, 47, 134.
Compound 2c: Yield 45%; 59% ee. [α]D20 = 8.8 (c 0.44, CHCl3).4 1
H
NMR (400 MHz CDCl3): δ = 7.26–7.39 (m, 5 H), 6.70–6.74 (d, J =
16.0 Hz, 1 H), 6.04–6.10 (dd, J = 16.0, 7.2 Hz, 1 H), 3.50 (m, 1 H),
1.50 (d,J = 7.2 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 135.7,
132.5, 128.7, 128.3, 126.5, 124.3, 120.9, 28.4, 19.1. MS (EI): m/z
(rel. intensity) = 157 (66) [M+], 158 (7), 156 (79), 142 (38), 129
(30), 115 (100), 102 (10), 91 (11), 89 (12), 77 (20), 63 (14), 51
(22). IR (film): ν = 2985 (w), 2242 (w), 1496 (w), 1449 (m), 1399
(m), 964 (m), 745 (s), 692 (s) cm–1. HPLC (Chiralcel OD-H,
hexane–2-PrOH = 95:5, 0.7 mL/min, 214 nm): tR (major) = 12.14
min; tR (minor) = 13.46 min. HRMS: m/z calcd for C11H10N [M+]:
157.0891; found: 157.0889.
20
Compound 1c: Yield 51%; 88% ee. [α]D = –75.8 (c 0.8, CHCl3).
1H NMR (400 MHz CDCl3): δ = 7.24–7.40 (m, 4 H), 6.63–6.67 (d,
J = 16.0 Hz, 1 H), 6.18–6.24 (dd, J = 16.0, 7.2 Hz, 1 H), 5.36 (m, 1
H), 3.92 (d,J = 6.8 Hz, 2 H), 1.97 (m, 1 H), 1.46 (d, J = 5.6 Hz, 3 H),
0.95 (d, J = 7.2 Hz, 6 H). MS (EI): m/z (rel. intensity) = 248 (8.0)
[M+], 205 (7), 192 (1), 148 (39), 131 (100), 115 (43), 105 (31), 91
(59), 77 (16), 57 (46), 51 (8). HPLC (Chiralcel OD-H, hexane–2-
PrOH = 99:1, 0.7 mL/min, 214 nm): tR (major) = 7.18 min; tR
(minor) = 7.80 min.
20
(6) For general reviews on kinetic resolution, see: (a) Kagan, H. B.;
Fiaud, J. C. Top. Stereochem. 1988, 18, 249. (b) Cook, G. R. Curr.
Org. Chem. 2000, 4, 869. (c) Keith, J. M.; Larrow, J. F.; Jacobsen, E.
N. Adv. Synth. Catal. 2001, 343, 5. (d) Vedejs, E.; Jure, M. Angew.
Chem. Int. Ed. 2005, 44, 3974. For some selected examples, see:
(e) Hayashi, T.; Yamamoto, A.; Ito, Y. J. Chem. Soc., Chem.
Commun. 1986, 1090. (f) Kagan, H. B.; Fiaud, J. C. Top. Stereo-
chem. 1988, 18, 249. (g) Gais, H.-J.; Spalthoff, N.; Jagusch, T.;
Frank, M.; Raabe, G. Tetrahedron Lett. 2000, 41, 3809.
(h) Longmire, J. M.; Wang, B.; Zhang, X. Tetrahedron Lett. 2000,
41, 5435. (i) Hughes, D. L.; Palucki, M.; Yasuda, N.; Reamer, R. A.;
Reider, P. J. J. Org. Chem. 2002, 67, 2762. (j) Lussem, B. J.; Gais, H.
J. J. Am. Chem. Soc. 2003, 125, 6066. (k) Faller, J. W.; Wilt, J. C.;
Parr, J. Org. Lett. 2004, 6, 1301. (l) Fischer, C.; Defieber, C.;
Suzuki, T.; Carreira, E. M. J. Am. Chem. Soc. 2004, 126, 1628.
(m) Onitsuka, K.; Matsushima, Y.; Takahashi, S. Organometallics
2005, 24, 6472. (n) Mao, B.; Ji, Y.-N.; Fañanás-Mastral, M.; Auke-
Meetsma, G. C.; Feringa, B. L. Angew. Chem. Int. Ed. 2012, 51,
3168.
(7) (a) Lei, B.-L.; Ding, C.-H.; Yang, X.-F.; Wan, X.-L.; Hou, X.-L. J. Am.
Chem. Soc. 2009, 131, 18250. (b) Hou, X.-L.; Zheng, B.-H. Org.
Lett. 2009, 11, 1789. (c) Lei, B.-L.; Zhang, Q.-S.; Yu, W.-H.; Ding,
Q.-P.; Ding, C.-H.; Hou, X.-L. Org. Lett. 2014, 16, 1944.
(8) (a) Tsuji, Y.; Yamada, N.; Tanaka, S. J. Org. Chem. 1993, 58, 16.
(b) Tsuji, Y.; Kusui, T.; Kojima, T.; Sugiura, Y.; Yamada, N.;
Tanaka, S.; Ebihara, M.; Kawamura, T. Organometallics 1998, 17,
4835. (c) Munemori, M.; Tsuji, H.; Uchida, K.; Suzuki, Y.; Isa, K.;
Minakawa, M.; Kawatsura, M. Synthesis 2014, 46, 2747.
Compound 2i: Yield 42%; 60% ee. [α]D = 8.4 (c 0.8, CHCl3).
1HNMR (400 MHz,CDCl3): δ = 7.21–7.26 (m, 1 H), 6.97 (d, J = 7.6
Hz, 1 H), 6.90 (s, 1 H), 6.83 (dd, J = 8.4, 2.4 Hz, 1 H), 6.66–6.70 (d,
J = 15.6 Hz, 1 H), 6.06 (dd, J = 16.0, 6.4 Hz, 1 H), 3.82 (m, 1 H),
3.51 (m, 1 H), 1.5 (d, J = 7.2 Hz, 3 H). 13C NMR (101 MHz, CDCl3):
δ = 159.8, 137.1, 132.4, 129.7, 124.6, 120.9, 119.1, 113.9, 111.9,
55.3, 28.4, 19.0. MS (EI): m/z (rel. intensity): 187 (100) [M+], 186
(57), 172 (23), 156 (22), 144 (94), 128 (20), 115 (48), 102 (24),
91 (22), 77 (22), 63 (23), 51 (18). IR (film): ν = 2938 (m), 2836
(m), 2241 (m), 1599 (s), 1579 (s), 1453 (m), 1263 (m), 1041 (m),
964 (s), 775 (s), 688 (s) cm–1. HPLC (Chiralpak PA-2, hexane–2-
PrOH = 99:1, 1.0 mL/min, 214 nm): tR (major) = 27.98 min; tR
(minor) = 31.74 min. HRMS: m/z calcd for C12H13NO [M+]:
187.0994; found: 187.0997.
Compound 1i: Yield 48%; 74% ee. [α]D20 = –60.4 (c 1.3, CHCl3). 1H
NMR (400 MHz,CDCl3): δ = 7.21–7.26 (m, 1 H), 6.97 (d, J = 7.6
Hz, 1 H), 6.90 (s, 1 H), 6.83 (dd, J = 8.0, 2.0 Hz, 1 H), 6.66–6.70 (d,
J = 16.0 Hz, 1 H), 6.06 (dd, J = 16.0, 6.4 Hz, 1 H), 5.36 (m, 1 H),
3.92 (d, J = 6.8 Hz, 1 H), 3.91 (s, 3 H), 1.97 (m, 1 H), 1.46 (d, J = 6.4
Hz, 2 H), 0.92 (d, J = 6.4 Hz, 9 H). MS (EI): m/z (rel. intensity):
278 (32) [M+], 235 (2), 178 (33), 161 (75), 145 (42), 135 (100),
129 (18), 117 (26), 91 (34), 77 (14), 57 (51). HPLC (Chiralpak OJ-
H, hexane–2-PrOH = 99.5:0.5, 0.7 mL/min, 214 nm): tR (major) =
23.67 min; tR (minor) = 29.92.
Compound 2p: Yield 39%; 43% ee. [α]D20 = 2.4 (c 0.85, CHCl3). 1H
NMR (400 MHz,CDCl3): δ = 7.25–7.40 (m, 5 H), 6.81–6.72 (d, J =
16.0 Hz, 1 H), 6.01 (dd, J = 16.0, 6.8 Hz, 1 H), 3.36 (m, 1 H), 1.67–
1.82 (m, 6 H), 1.19–1.26 (m, 5 H). 13C NMR (101 MHz, CDCl3):
δ = 135.8, 133.9, 128.7, 128.1, 126.5, 122.1, 119.4, 41.1, 40.8,
31.0, 29.6, 26.0, 25.8. MS (EI): m/z (rel. intensity): 225 (8) [M+],
143 (100), 128 (2), 115 (25), 102 (2), 91 (4), 83 (13), 65 (3), 55
(46). IR (film): ν = 2922 (m), 2854 (m), 2233 (w), 1449 (m), 974
(9) Tsuji reported one example in ref. 8b.
(10) General Procedure for Kinetic Resolution
[Pd(η3-C3H5)Cl]2 (2.0 mg, 0.006 mmol) and ligand (R,R)-L (8.0
mg, 0.006 mmol) and toluene (1.0 mL) were added into a dry
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 1510–1514