I
N. Someshwar et al.
Letter
Synlett
(2) (a) Akiyama, T. Chem. Rev. 2007, 107, 5744. (b) Tereda, M. Chem.
Commun. 2008, 4097. (c) Čorić, I.; List, B. Nature 2012, 483, 315.
(3) Teichert, J. F.; Feringa, B. L. Angew. Chem. Int. Ed. 2010, 49, 2486.
(4) Okano, K. Tetrahedron 2011, 67, 2483.
(5) Seebach, D.; Beck, A. K.; Heckel, A. Angew. Chem. Int. Ed. 2001,
40, 92.
(6) (a) Hua, Z.; Vassar, V. C.; Ojima, I. Org. Lett. 2003, 5, 3831.
(b) Shi, C.; Chien, C. W.; Ojima, I. Chem. Asian J. 2011, 6, 674.
(7) (a) Pu, L. Chem. Rev. 1998, 98, 2405. (b) Pu, L.; Yu, B.-H. Chem.
Rev. 2001, 101, 757.
(8) (a) Chen, X.-H.; Xu, X.-Y.; Liu, H.; Cun, L.-F.; Gong, L.-Z. J. Am.
Chem. Soc. 2006, 128, 14802. (b) Li, X.; Jia, X.; Lu, G.; Au-Yeung,
T. T.-L.; Lam, K.-H.; Lo, T. W. H.; Chan, A. S. C. Tetrahedron: Asym-
metry 2003, 14, 2687.
(9) (a) Desai, A. A.; Wulff, W. D. Synthesis 2010, 3670. (b) Bao, J.;
Wulff, W. D.; Rheingold, A. L. J. Am. Chem. Soc. 1993, 115, 3814.
(10) (a) Akiyama, T.; Saitoh, Y.; Morita, H.; Fuchibe, K. Adv. Synth.
Catal. 2005, 347, 1523. (b) Voituriez, A.; Charette, A. B. Adv.
Synth. Catal. 2006, 348, 2363. (c) Lam, H. W. Synthesis 2011,
2011. (d) Teller, H.; Corbet, M.; Mantilli, L.; Gopakumar, G.;
Goddard, R.; Thiel, W.; Fürstner, A. J. Am. Chem. Soc. 2012, 134,
15331.
(11) (a) Liu, Y.; Ding, K. J. Am. Chem. Soc. 2005, 127, 10488. (b) Dong,
K.; Wang, Z.; Ding, K. J. Am. Chem. Soc. 2012, 134, 12474.
(c) Stemper, J.; Isaac, K.; Duret, V.; Retailleau, P.; Voituriez, A.;
Betzer, J.-F.; Marinetti, A. Chem. Commun. 2013, 49, 6084.
(d) Gnanamani, E.; Someshwar, N.; Ramanathan, C. R. Adv.
Synth. Catal. 2014, 356, 2219.
(21) Arylfluorenes 19a–g; General Procedure
mixture of the appropriate (3-methoxy-2-naphthyl)(dia-
A
ryl)methanol 13a–g (0.5 mmol) and NaHSO4/SiO2 (250 mg) in
dry DCE (10 mL) was heated at 90 °C with vigorous stirring for
24 hours under N2. The mixture was then cooled to r.t., filtered,
and concentrated under reduced pressure. The residue was
purified by column chromatography [silica gel, hexane–EtOAc
(99:1)] to give the arylfluorene 19a–g in pure form.
6-Methoxy-7-phenyl-7H-benzo[c]fluorene (19a)
White solid; yield: 114 mg (71%); mp 168–170 °C. IR (KBr):
2922, 2846, 1592, 1559, 1457, 824, 735, 695 cm–1. 1H NMR (400
MHz, CDCl3): δ = 8.67 (d, J = 8.0 Hz, 1 H), 8.30 (d, J = 8.0 Hz, 1 H),
7.79–7.77 (m, 1 H), 7.46–7.35 (m, 3 H), 7.29–7.27 (m, 1 H),
7.21–7.17 (m, 2 H), 7.14–7.09 (m, 2 H), 7.04–6.98 (m, 3 H), 5.09
(s, 1 H), 3.70 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 155.0,
150.0, 141.7, 141.0, 137.9, 137.8, 136.0, 129.7, 128.4, 128.3,
128.1, 128.0, 127.3, 126.8, 126.5, 125.9, 125.4, 125.3, 124.4,
124.0, 123.1, 106.0, 55.5, 53.0. HRMS-ESI: m/z [M + H]+ calcd for
C
24H19O: 323.1436; found: 323.1425.
(22) CCDC No. 1537731 and 1537733 contain the supplementary
crystallographic data for compounds 19f and 12a. The data can
be obtained free of charge from The Cambridge Crystallo-
(23) (a) Someshwar, N.; Ramanathan, C. R. Tetrahedron: Asymmetry
2015, 26, 1209. (b) Ramanathan, C. R.; Someshwar, N. A. IN
2418/del/2014, 2014.
(24) (a) Belokon, Yu. N.; Maleev, V. I.; Moskalenko, M. A.;
Samoilichenko, Yu. V.; Peregudov, A. S.; Tsaloev, A. T. Russ.
Chem. Bull. 2013, 62, 1371. (b) Li, X.; Hewgley, J. B.; Mulrooney,
C. A.; Yang, J.; Kozlowski, M. C. J. Org. Chem. 2003, 68, 5500.
(25) (2R)-2-Phenyl-1,2,3,4-tetrahydroquinoline (25); Typical Pro-
cedure
(12) Vougioukalakis, G. C.; Roubelakis, M. M.; Orfanopoulos, M.
J. Org. Chem. 2010, 75, 4124.
(13) Chandrasekhar, V.; Narayanan, R. S.; Thilagar, P. Organometallics
2009, 28, 5883.
(14) Mahindaratne, M. P. D.; Wimalasena, K. J. Org. Chem. 1998, 63,
2858.
(15) Wang, J.; Wan, W.; Jiang, H.; Gao, Y.; Jiang, X.; Lin, H.; Zhao, W.;
Hao, J. Org. Lett. 2010, 12, 3874.
The quinoline 23 (25.6 mg, 0.125 mmol), catalyst (+)-22 (15.3
mg, 0.025 mmol, 20 mol%), Hantzsch dihydropyridine 24 (76
mg, 0.3 mmol), and toluene (3 mL) were added under N2 to test
tube equipped with a side arm. The resulting yellow solution
was stirred at r.t. for 24 h. The solvent was evaporated in vacuo,
and the residue was purified by column chromatography (silica
gel) to give a colorless oil; yield: 23 mg (88%; 22% ee); IR (neat):
(16) Khenkin, A. M.; Neumann, R. J. Am. Chem. Soc. 2002, 124, 4198.
(17) (a) Li, G.; Wang, E.; Chen, H.; Li, H.; Liu, Y.; Wang, P. G. Tetrahe-
dron 2008, 64, 9033. (b) Wu, Y.; Zhang, J.; Bo, Z. Org. Lett. 2007,
9, 4435. (c) Xia, C.; Advincula, R. C. Macromolecules 2001, 34,
6922. (d) Xie, L.; Fu, T.; Hou, X.; Tang, C.; Hua, Y.; Wang, R. J.;
Fan, Q.; Peng, B.; Wei, W.; Huang, W. Tetrahedron Lett. 2006, 47,
6421. (e) Wong, K.-. T.; Chi, L.-C.; Huang, S.-C.; Liao, Y.-L.; Liu,
Y.-H.; Wang, Y. Org. Lett. 2006, 8, 5029.
(18) Chen, J.-J.; Onogi, S.; Hsieh, Y.-C.; Hsia, C.-C.; Higashibayashi, S.;
Sakurai, H.; Wu, Y.-T. Adv. Synth. Catal. 2012, 354, 1551.
(19) (a) Li, Q.; Xu, W.; Hu, J.; Chen, X.; Zhang, F.; Zheng, H. RSC Adv.
2014, 4, 27722. (b) Teng, M.-y.; Liu, Y.; Li, S.-l.; Huang, G.; Jiang,
J.; Wang, L. RSC Adv. 2013, 3, 9016.
3403, 2922, 1605, 1487, 1112, 749 cm–1 1H NMR (400 MHz,
.
CDCl3): δ = 7.58–7.44 (m, 5 H), 7.22–7.18 (m, 2 H), 6.85 (td, J =
7.6, 1.2 Hz, 1 H), 6.68 (d, J = 7.6 Hz, 1 H), 4.58 (dd, J = 9.2, 3.2 Hz,
1 H), 4.14 (s, 1 H), 3.13–3.05 (m, 1 H), 2.93–2.87 (m, 1 H), 2.32–
2.25 (m, 1 H), 2.21–2.17 (m, 1 H). 13C NMR (100 MHz, CDCl3)
δ = 144.85, 144.72, 129.29, 128.56, 127.41, 126.90, 126.56,
120.81, 117.14, 114.00, 56.18, 30.97, 26.34. Chiral HPLC: (Chi-
ralcel OD-H (4.6 × 250 mm); Mobile phase: hexanes–i-PrOH),
flow rate: 0.6 mL/min, λ = 254 nm: tR(S) = 20.13 min, tR(R) =
27.16 min.
(20) Sato, Y.; Aoyama, T.; Tokido, T.; Kodomari, M. Tetrahedron 2012,
68, 7077.
(26) Guo, Q.-S.; Du, D.-M.; Xu, J. Angew. Chem. Int. Ed. 2008, 47, 759.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–I