J. Stec et al. / Tetrahedron Letters 53 (2012) 1112–1115
1115
(major enantiomer); syn-isomer Rt 11.4 min (minor enantiomer)
References and notes
and 13.2 min (major enantiomer).
1. (a) Yamamoto, H. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I.,
Eds., Second ed.; Pergamon: Oxford, UK, 1991; pp 81–98. Vol. 2, Ch. 1.3; (b)
Ding, C. –H.; Hou, X. –L. Chem. Rev. 2011, 111, 1914–1937.
anti Diastereoisomer of 26a
2. Negishi, E.; Akiyoshi, K.; O’Connor, B.; Takagi, K.; Wu, G. Z. J. Am. Chem. Soc.
1989, 111, 3089–3091.
3. Kocienski, P.; Barber, C. Pure Appl. Chem. 1990, 62, 1933–1940.
4. Harada, T.; Katsuhira, T.; Osada, A.; Iwazaki, K.; Maejima, K.; Oku, A. J. Am.
Chem. Soc. 1996, 118, 11377–11390.
5. Zweifel, G.; Backlund, S. J.; Leung, T. J. Am. Chem. Soc. 1978, 100, 5561–5562.
6. Carrik, D.; Carboni, B.; Vaultier, M. Tetrahedron Lett. 1995, 36, 8209–8212.
7. Canales, E.; Gonzalez, A. Z.; Soderquist, J. A. Angew. Chem., Int. Ed. 2007, 46,
397–399.
8. (a) Luker, T.; Whitby, R. J. Tetrahedron Lett. 1994, 35, 785–788; (b) Gordon, G. J.;
Whitby, R. J. Chem. Commun. 1997, 1321–1322.
9. (a) Kasatkin, A.; Whitby, R. J. J. Am. Chem. Soc. 1999, 121, 7039–7049; (b)
Kasatkin, A. N.; Whitby, R. J. Tetrahedron Lett. 1999, 40, 9353–9357; (c)
Kasatkin, A. N.; Whitby, R. J. Tetrahedron Lett. 2000, 41, 6211–6216.
10. For alkynyl addition to aldehydes and ketones, see: Frantz, D. E.; Carreira, E. M.
In Stereoselective Synthesis; Molander, G. A., Ed.; Thieme, 2011; pp 497–516.
Vol. 2, Ch. 2.10.1; For selected examples of asymmetric reduction of ynones,
see: (a) Midland, M. M.; Tramontano, A.; Kazubski, A.; Graham, R. S.; Tsai, D. J.
S.; Cardin, D. B. Tetrahedron 1984, 40, 1371–1380; (b) Matsumura, K.;
Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738–8739;
(c) Eagon, S.; DeLieto, C.; McDonald, W. J.; Haddenham, D.; Saavedra, J.; Kim, J.;
Singaram, B. J. Org. Chem. 2010, 75, 7717–7725.
1H NMR (400 MHz, CDCl3): d (ppm) = 7.45–7.24 (5H, m), 4.43
(1H, dd, J = 6.9, 3.5 Hz, CHOH), 2.76 (1H, m, CHMe), 2.64 (1H, d,
J = 3.5 Hz, OH), 2.21 (2H, td, J = 6.9, 2.0 Hz, CH2C„C), 1.51 (2H,
quin, J = 7.1 Hz), 1.43–1.20 (10H, m), 1.07 (3H, d, J = 6.9 Hz), 0.90
(3H, t, J = 6.6 Hz). 13C NMR (100.5 MHz, CDCl3): d (ppm) = 141.68
(C), 128.16 (2CH), 127.76 (CH), 126.67 (2CH), 84.18 (C), 80.70 (C),
77.75 (CH), 35.67 (CH), 31.81 (CH2), 29.16 (CH2), 29.07 (CH2),
28.93 (CH2), 28.85 (CH2), 22.63 (CH2), 18.72 (CH2), 17.81 (CH3),
14.07 (CH3). HRMS (EI): Found: [MꢁH2O]+, 254.2040. [C19H26]+ re-
quires: 254.2034. LRMS (CI): m/z: 273 ([M+H]+, 54%), 255
([(M+H)+ꢁH2O], 72%).
A pure sample of the minor syn-diastereoisomer was obtained by
HPLC (4.6 ꢂ 250 mm PartisilÒ 60 Å 5
l
m SiOH column, 0.7% iPrOH in
hexanes, 1 mL/min; anti-isomer Rt 5.6 min; syn-isomer Rt 6.8 min.):
1H NMR (400 MHz, CDCl3): d (ppm) = 7.44-7.22 (5H, m), 4.71 (1H, m,
CHOH), 2.86 (1H, m, CHMe), 2.25 (1H, d, J = 3.0 Hz, OH), 2.15 (2H, td,
J = 6.9, 1.8 Hz, CH2C„C), 1.46 (2H, quin, J = 7.1 Hz), 1.37–1.21 (10H,
m), 1.07 (3H, d, J = 7.1 Hz), 0.90 (3H, t, J = 6.3 Hz). 13C NMR
(100.5 MHz, CDCl3): d (ppm) = 141.52 (C), 127.99 (2CH), 127.51
(CH), 126.49 (2CH), 83.55 (C), 81.28 (C), 76.43 (CH), 34.35 (CH),
31.84 (CH2), 29.18 (CH2), 29.11 (CH2), 28.93 (CH2), 28.82 (CH2),
22.65 (CH2), 18.72 (CH2), 15.86 (CH3), 14.11 (CH3).
11. Siegel, H. Topics Curr. Chem. 1982, 106, 55–78.
12. Duraisamy, M.; Walborsky, H. M. J. Am. Chem. Soc. 1984, 106, 5035–5037.
13. Topolski, M.; Duraisamy, M.; Rachon, J.; Gawronski, J.; Gawronska, K.;
Goedken, V.; Walborsky, H. M. J. Org. Chem. 1993, 58, 546–555.
14. Kobrich, G.; Ansari, F. Chem. Ber. 1967, 100, 2011–2020.
15. Hoffmann, R. W.; Nell, P. G.; Leo, R.; Harms, K. Chem. Eur. J. 2000, 6, 3359–3365.
16. Blakemore, P. R.; Marsden, S. P.; Vater, H. D. Org. Lett. 2006, 8, 773–776.
17. Marshall, J. A. J. Org. Chem. 2007, 72, 8153–8166.
18. (a) Ito, H.; Nakamura, T.; Taguchi, T.; Hanzawa, Y. Tetrahedron 1995, 51, 4507–
4518; (b) Zhang, H.; Fu, X.; Chen, J.; Wang, E.; Liu, Y.; Li, Y. J. Org. Chem. 2009,
74, 9351–9358.
Acknowledgments
19. Schwartz, J.; Labinger, J. A. Angew. Chem., Int. Ed. 1976, 15, 333–340.
20. Kondakov, D. Y.; Negishi, E. J. Am. Chem. Soc. 1995, 117, 10771–10772.
We thank GlaxoSmithKline, the EPSRC and ERDF (IS:CE-Chem &
InterReg IVa program 4061) for funding this work.