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S. Guillarme, A. Haudrechy / Tetrahedron Letters 46 (2005) 3175–3178
120(11), 1845–1851; (c) Tang, C.-J.; Wu, Y. Helv. Chim.
Acta 2004, 87(3), 667–673.
(quat C), 138.7 (quat C), 138.6 (quat C), 136.5 (@CH),
128.9 (CH), 128.8 (CH, 2C overlap), 128.7 (CH), 128.6
(CH), 128.5 (CH), 128.3 (CH), 128.1 (CH), 128.0 (CH),
120.3 (@CH2), 87.4 (quat C), 83.4 (CH–O), 81.9 (CH–O),
81.0 (CH–O), 79.5 (quat C), 75.7 (CH2–O), 75.0 (CH2–O),
70.6 (CH2–O), 64.0 (CH–O), 22.4 (CH2), 21.3 (CH2), 14.0
(CH3). HRMS (ES) Calcd for C32H36O4Na: 507.2511.
Found: 507.2501; (c) syn 6–3: 1H NMR (250 MHz,
CDCl3): d 7.38–7.15 (m, 15H, Har), 6.06–5.80 (m, 1H,
@CH), 5.43 (dd, 2H, @CH2, J = 10.3, 17.0 Hz), 4.80–4.45
(m, 7H, CH–O and CH2–O), 4.20–4.05 (m, 2H, CH–O),
3.90–3.80 (m, 1H, CH–O), 2.52 (br s, 1H, OH), 2.22 (t, 2H,
CH2, J = 7.1 Hz), 1.55–1.45 (m, 2H, CH2); 1.40–1.22 (m,
4H, CH2), 0.86 (t, 3H, CH3, J = 7.1 Hz). 13C NMR
(62.5 MHz, CDCl3): 138.9 (quat C), 138.6 (quat C), 138.3
(quat C), 136.1 (@CH), 128.7 (CH), 128.5 (CH, 2C
overlap), 128.3 (CH, 2C overlap), 128.1 (CH), 127.8 (CH,
2C overlap), 127.7 (CH), 120.1 (@CH2), 87.2 (quat C), 83.1
(CH–O), 81.6 (CH–O), 80.8 (CH–O), 79.0 (quat C), 75.4
(CH2–O), 75.0 (CH2–O), 70.3 (CH2–O), 63.7 (CH–O), 31.2
(CH2), 28.3 (CH2), 22.3 (CH2), 18.9 (CH2), 14.1 (CH3).
HRMS (ES) Calcd for C34H40O4Na: 535.2824. Found:
535.2810; (d) syn 6–4: 1H NMR (250 MHz, CDCl3): d
7.27–7.16 (m, 15H, Har), 5.88 (ddd, 1H, @CH, J = 7.6, 9.6,
17.5 Hz), 5.46 (dd, 2H, @CH2, J = 9.6, 17.5 Hz), 4.72–4.48
(m, 6H, CH2–O and CH–O), 4.20 (d, 1H, CH2–O,
J = 11.6 Hz), 3.98 (dd, 1H, CH–O, J = 6.1, 7.6 Hz), 3.82–
3.72 (m, 2H, CH–O), 2.60 (d, 1H, OH, J = 6.1 Hz), 0.10 (s,
9H, CH3). 13C NMR (62.5 MHz, CDCl3): 138.6 (quat C),
138.4 (quat C), 138.3 (quat C), 136.1 (@CH), 128.6 (CH,
2C overlap), 128.5 (CH, 2C overlap), 128.4 (CH), 128.3
(CH), 127.9 (CH, 2C overlap), 127.8 (CH), 120.1 (@CH2),
104.1 (quat C), 91.1 (quat C), 82.7 (CH–O), 81.8 (CH–O),
80.9 (CH–O), 75.6 (CH2–O), 75.1 (CH2–O), 70.4 (CH2–O),
63.9 (CH–O), 0.0 (CH3). HRMS (ES) Calcd for
C32H38O4SiNa: 537.2454. Found: 537.2437; (e) syn 6–6:
1H NMR (250 MHz, CDCl3): d 7.30–7.10 (m, 15H, Har),
5.94–5.76 (m, 1H, @CH), 5.46 (dd, 2H, @CH2, J = 10.9,
16.3 Hz), 4.70–4.44 (m, 6H, CH2–O and CH–O), 4.24 (d,
1H, CH2–O, J = 1.7 Hz), 4.17 (d, 1H, CH2–O,
J = 11.6 Hz), 3.98 (dd, 1H, CH–O, J = 6.1, 7.4 Hz), 3.80–
3.70 (m, 2H, CH–O), 2.52 (d, 1H, OH, J = 5.7 Hz), 0.78 (s,
9H, CH3), 0.0 (s, 6H, CH3). 13C NMR (62.5 MHz, CDCl3):
138.8 (quat C), 138.7 (quat C), 138.6 (quat C), 136.4
(@CH), 129.0 (CH), 128.8 (CH), 128.7 (CH), 128.6 (CH),
128.5 (CH), 128.3 (CH), 128.1 (CH, 2C overlap), 128.0
(CH), 120.4 (@CH2), 85.2 (quat C), 84.0 (quat C), 82.8
(CH–O), 81.8 (CH–O), 81.0 (CH–O), 75.7 (CH2–O), 75.3
(CH2–O), 70.6 (CH2–O), 63.7 (CH–O), 52.2 (CH2–O), 26.2
(CH3), 18.7 (quat C), 0.0 (CH3). HRMS (ES) Calcd for
C36H47O5SiNa: 587.3193. Found: 587.3181.
7. Frankowski, A.; Deredas, D.; Streith, J.; Tschamber, T.
Tetrahedron 1998, 54(31), 9033–9042.
8. Configurations were determined by derivatization to
1
the corresponding Mosher esters with H NMR analysis.
9. Imamoto, T.; Sugiura, Y.; Tagiyama, N. Tetrahedron Lett.
1984, 25(38), 4233–4236.
10. Ishiyama, H.; Takemura, T.; Tsuda, M.; Kobayashi, J.
Tetrahedron 1999, 55(15), 4583–4594.
11. Typical procedure (example for entry 12): Zinc(II) chloride
(102.4 mg, 0.751 mmol) was fused under high vacuum.
After cooling, anhydrous diethyl ether (1.5 mL) was then
introduced under argon. To this solution was added a
solution of lithium phenylacetylide (prepared from phen-
ylacetylene (51.1 mg, 0.5 mmol) and n-BuLi (0.31 mL,
0.5 mmol, 1.6 M solution in hexanes) in diethyl ether
(2 mL)) at 0 °C. The solution was stirred for 45 min at
0 °C before the addition of a solution of aldehyde 1
(60.2 mg, 0.145 mmol) in diethyl ether (1 mL). The solu-
tion was stirred for 2.5 h at 0 °C, diluted with diethyl ether
and quenched with a saturated NH4Cl solution. The
organic layer was washed with brine, dried, and evapo-
rated under reduced pressure. Purification by silica gel
column chromatography (petroleum ether/ethyl acetate:
95/5 ! 90/10) led to 5 (59.3 mg, 0.114 mmol, 79%) as a
mixture of 1,2-syn- and 1,2-anti-isomers in a 93:7 ratio.
12. (a) Dolence, E. K.; Adamczyk, M.; Watt, D. S.; Russell,
B. G.; Horn, D. H. S. Tetrahedron Lett. 1987, 26(9), 1189–
1192; (b) Caderas, C.; Lett, R.; Overman, L. E.; Rabino-
witz, M. H.; Robinson, L. A.; Sharp, M. J.; Zablocki, J.
J. Am. Chem. Soc. 1996, 118(38), 9073–9082; (c) Overman,
L. E.; Robinson, L. A.; Zablocki, J. J. Am. Chem. Soc.
1992, 114(1), 368–369.
13. Evans, D. A.; Halstead, D. P.; Allison, B. D. Tetrahedron
Lett. 1999, 40, 4461–4462.
14. (a) syn 6–1: 1H NMR (250 MHz, CDCl3): d 7.42–7.21 (m,
20H, Har), 5.97 (ddd, 1H, @CH, J = 7.6, 10.2, 17.4 Hz),
5.46 (dd, 2H, @CH2, J = 10.2, 17.4 Hz), 4.84 (d, 1H, CH–
O, J = 3.6 Hz), 4.81–4.62 (m, 6H, CH2–O), 4.12 (dd, 1H,
CH–O, J = 6.5, 7.6 Hz), 4.00–3.89 (m, 2H, CH–O), 2.81 (br
s, 1H, OH). 13C NMR (62.5 MHz, CDCl3): 138.3 (quat C),
138.1 (quat C), 138.0 (quat C), 135.9 (@CH), 131.6 (CH),
128.4 (CH, 2C overlap), 128.3 (CH, 2C overlap), 128.2
(CH, 2C overlap), 128.1 (CH), 128.0 (CH), 127.7 (CH, 2C
overlap), 127.6 (CH), 127.5 (CH), 122.4 (quat C), 119.9
(@CH2), 88.1 (quat C), 86.0 (quat C), 82.6 (CH–O), 81.5
(CH–O), 80.6 (CH–O), 75.3 (CH2–O), 74.8 (CH2–O), 70.1
(CH2–O), 63.7 (CH–O). HRMS (ES) Calcd for
1
C35H34O4Na: 541.2355. Found: 541.2369; (b) syn 6–2: H
NMR (250 MHz, CDCl3): d 7.38–7.20 (m, 15H, Har),
6.05–5.85 (m, 1H, @CH), 5.46 (dd, 2H, @CH2, J = 11.1,
16.3 Hz), 4.74 (d, 1H, CH–O, J = 2.9 Hz), 4.71–4.52 (m,
6H, CH2–O), 4.29 (dd, 1H, CH–O, J = 5.3, 6.3 Hz), 3.90–
3.76 (m, 2H, CH–O), 2.55 (br s, 1H, OH), 2.20 (dt, 2H,
CH2, J = 2.1, 7.3 Hz), 1.61–1.44 (m, 2H, CH2), 0.97 (t, 3H,
CH3, J = 7.3 Hz). 13C NMR (62.5 MHz, CDCl3): 138.9
15. (a) Herrmann, J. L.; Berger, M. H.; Schlessinger, R. H.
J. Am. Chem. Soc. 1979, 101(6), 1544–1549; (b) Midland,
M. M.; Tramontano, A.; Cable, J. R. J. Org. Chem. 1980,
45(1), 28–29.
16. Shahi, S. P.; Koide, K. Angew. Chem. 2004, 43(19), 2525–
2527.