6576
T. Soeta et al. / Tetrahedron 63 (2007) 6573–6576
4.1.5. (L)-(R)-5-(Naphth-2-yl)cyclohexenone 12d (R1=
2-naph) (entry 5). Chromatography (hexane/diethyl
ether¼20:1) gave a 87:13 trans/cis mixture of (ꢁ)-3-ethyl-
5-(naphtha-2-yl)cyclohexanone 13 (R1¼2-naph, R2¼Et)
(162 mg, 64% yield, 87% ee (trans)) as a colorless oil of
[a]2D5 +5.90 (c 1.14, CHCl3) and (ꢁ)-(R)-5-(naphth-2-yl)-
cyclohexenone 12d (71 mg, 33% yield, 95% ee) as solid of
mp 107–109 ꢀC and [a]D25 ꢁ73.2 (c 0.56, CHCl3).
€
Hoffmann-Roder, A. Synthesis 2001, 171–196; (e) Kanai, M.;
Shibasaki, M. Catalytic Asymmetric Synthesis; Ojima, I., Ed.;
Wiley-VCH: Weinheim, 2000; p 569; (f) Tomioka, K. Synthesis
1990, 541–549.
2. (a) Jacobsen, E. N. Acc. Chem. Res. 2000, 33, 421–431; (b)
Bellemin-Laponnaz, S.; Tweddell, J.; Ruble, G.; Breitling,
F. M.; Fu, G. C. Chem. Commun. 2000, 1009–1010; (c) Yun,
J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 767–774; (d)
Feng, X.; Shu, L.; Shi, Y. J. Am. Chem. Soc. 1999, 121,
11002–11003; (e) Ogasawara, K. Pure Appl. Chem. 1994, 66,
2119–2122.
3. (a) Kuriyama, M.; Nagai, K.; Yamada, K.; Miwa, Y.; Taga, T.;
Tomioka, K. J. Am. Chem. Soc. 2002, 124, 8932–8939; (b)
Kuriyama, M.; Tomioka, K. Tetrahedron Lett. 2001, 42, 921–
923.
(ꢁ)-13 (R1¼2-Naph, R2¼Et): Major trans- and cis-13 were
determined to have 87% ee and 90% ee by HPLC (Daicel
Chiralcel OD-H, hexane/i-PrOH¼10:1, 0.5 mL/min,
254 nm, trans isomer: major 22 min and minor 24 min, cis
isomer: major 31 min and minor 26 min). The ratio of
trans/cis¼87:13 was determined by the integration area of
1
1H NMR signals of the trans Me (t) and the cis Me (t)). H
4. Chen, Q.; Kuriyama, M.; Soeta, T.; Hao, X.; Yamada, K.;
Tomioka, K. Org. Lett. 2005, 7, 4439–4441.
NMR: 0.89 (0.87H, t, J¼7.3 Hz, trans), 0.96 (0.13H, t,
J¼7.3 Hz, cis), 1.38–1.51 (2H, m, trans+cis), 1.95–2.28
(4H, m, trans+cis), 2.57–2.78 (3H, m, trans+cis), 3.50 (1H,
m, trans+cis), 7.37–7.83 (7H, m, trans+cis). 13C NMR:
11.1 (cis), 11.4 (trans), 27.0 (trans), 29.9 (cis), 35.8 (trans),
36.8 (trans), 39.2 (cis), 39.5 (trans), 39.9 (cis), 43.8 (cis),
46.7 (trans), 47.1 (trans), 47.3 (cis), 48.7 (cis), 124.5 (cis),
125.0 (trans), 125.6 (trans), 126.1 (trans), 127.1 (trans),
127.5 (trans), 128.2 (trans), 132.2 (trans), 132.3 (cis),
133.4 (trans), 141.7 (trans), 143.1 (cis), 211.7 (trans). IR
(neat): 1720. EIMS m/z: 252 (M+). HRMS m/z calcd for
C18H20O: 252.1514. Found: 212.1516.
5. (a) Chen, Q.; Soeta, T.; Kuriyama, M.; Yamada, K.; Tomioka,
K. Adv. Synth. Catal. 2006, 348, 2604–2608; (b) Urbaneja,
L. M.; Krause, N. Tetrahedron: Asymmetry 2006, 17, 494–496.
6. Tomioka, K. Pure Appl. Chem. 2006, 78, 2029–2034.
7. Soeta, T.; Selim, K.; Kuriyama, M.; Tomioka, K. Adv. Synth.
Catal. 2007, 349, 629–635.
8. Asymmetric reactions with organozinc reagents: (a) Valleix, F.;
Nagai, K.; Soeta, T.; Kuriyama, M.; Yamada, K.; Tomioka, K.
Tetrahedron 2005, 61, 7420–7424; (b) Soeta, T.; Kuriyama, M.;
Tomioka, K. J. Org. Chem. 2005, 70, 297–300; (c) Kuriyama,
M.; Soeta, T.; Hao, X.; Chen, Q.; Tomioka, K. J. Am. Chem.
Soc. 2004, 126, 8128–8129; (d) Soeta, T.; Nagai, K.;
Fujihara, H.; Kuriyama, M.; Tomioka, K. J. Org. Chem.
2003, 68, 9723–9727; (e) Nagai, K.; Fujihara, H.; Kuriyama,
M.; Yamada, K.; Tomioka, K. Chem. Lett. 2002, 8–9; (f)
Fujihara, H.; Nagai, K.; Tomioka, K. J. Am. Chem. Soc.
2000, 122, 12055–12056; (g) Mori, T.; Kosaka, K.;
Nakagawa, Y.; Nagaoka, Y.; Tomioka, K. Tetrahedron:
Asymmetry 1998, 9, 3175–3178.
(ꢁ)-(R)-12d: The ee was determined to be 95% by HPLC
(Daicel Chiralcel OD-H, hexane/i-PrOH¼3:1, 0.5 mL/min,
254 nm, major 25 min and minor 20 min). The absolute con-
figuration was determined to be R by the specific rotation. 1H
NMR: 2.60–2.82 (m, 4H), 3.51 (m, 1H), 6.16 (d, J¼10 Hz,
1H), 7.06 (m, 1H), 7.37 (d, J¼8.6 Hz, 1H), 7.45–7.50 (m,
2H), 7.66 (s, 1H), 7.80–7.84 (m, 3H). 13C NMR (CDCl3):
33.5, 41.0, 44.8, 125.0, 125.2, 125.8, 126.3, 127.7, 127.8,
128.5, 129.8, 132.5, 133.5, 140.6, 149.4, 199.1. IR (Nujol):
1662. EIMS m/z: 222 (M+). Anal. Calcd for C16H14O: C,
86.45; H, 6.35. Found: C, 86.25; H, 6.49.
9. Asymmetric reactions with Grignard reagents: Nakagawa, Y.;
Matsumoto, K.; Tomioka, K. Tetrahedron 2000, 56, 2857–
2863 and references cited therein.
10. (a) Naasz, R.; Arnold, L. A.; Minnaard, A. J.; Feringa, B. L.
Angew. Chem., Int. Ed. 2001, 40, 927–930; (b) Imbos, R.;
Minnaard, A. J.; Feringa, B. L. Tetrahedron 2001, 57, 2485–
2489.
Acknowledgements
11. Urbaneja, L. M.; Alexakis, A.; Krause, N. Tetrahedron Lett.
2002, 43, 7887–7890.
12. (a) Sarakinos, G.; Corey, E. J. Org. Lett. 1999, 1, 811–814; (b)
Asaoka, M.; Shima, K.; Takei, H. Tetrahedron Lett. 1987, 28,
5669–5672.
This research was partially supported by the 21st Century
Center of Excellence Program ‘Knowledge Information
Infrastructure for Genome Science’ and a Grant-in-Aid for
Scientific Research on Priority Areas ‘Advanced Molecular
Transformations’ from the Ministry of Education, Culture,
Sports, Science and Technology, Japan.
13. (a) Yamamoto, Y. Methoden Org. Chem.; Helmchen, G.,
Houben, J., Wely, T., Eds.; Georg Thieme: Stuttgart, 1995;
Vol. E21b, pp 2041–2067; (b) Lipshutz, B. H.; Sengupta, S.
Org. React. 1992, 41, 135–631; (c) Corey, E. J.; Hannon,
F. J. Tetrahedron Lett. 1990, 31, 1393–1396; (d) Deslong-
champs, P. Stereoelectronic Effects in Organic Chemistry;
Pergamon: Oxford, 1983; (e) House, H. O.; Umen, M. J.
J. Org. Chem. 1973, 38, 1000–1003.
14. (a) For 13a: Marques, F. A.; Lenz, C. A.; Simonelli, F.; Maia,
B. H. L. N. S.; Vellasco, A. P.; Eberlin, M. N. J. Nat. Prod.
2004, 67, 1939–1941; (b) For 13b–d: Shull, B. K.; Sakai, T.;
Nichols, J. B.; Koreeda, M. J. Org. Chem. 1997, 62, 8294–8303.
15. Allinger, N. L.; Riew, C. K. J. Org. Chem. 1975, 40, 1316–1321.
References and notes
1. (a) Tomioka, K. Comprehensive Asymmetric Catalysis;
Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer:
Berlin, 2004; Supplement to Chapter 31.1, pp 109–124; (b)
Hayashi; T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829–
2844; (c) Feringa, B. L.; Naasz, R.; Imbos, R.; Arnold, L. A.
Modern Organocopper Chemistry; Krause, N., Ed.;
Wiley-VCH: Weinheim, 2002; Chapter 7; (d) Krause, N.;