542
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3. The triple salt 2·KHSO5·KHSO4·K2SO4 was used as a source for potassium monoperoxysulfate.
4. Nicolaou, K. C.; Prasad, C. V. C.; Ogilvie, W. W. J. Am. Chem. Soc. 1990, 112, 4988–4989.
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7. General procedure for the preparation of epoxides 2 and 3: A 0.075 M solution of dimethyldioxirane (80 mL, 6.0 mmol)
was slowly added to a cooled (0°C) solution of endo-dicyclopentadiene 1 (2.0 mL, 14.8 mmol) in CH2Cl2 (20 mL) under an
argon atmosphere. The stirring was continued at 0°C for 5 h. The solvents were evaporated under reduced pressure and the
residue was chromatographed (flash silica gel: CH2Cl2:pet. ether=2:1) to afford epoxide 2 (310 mg, 35% yield) and epoxide
3 (355 mg, 40% yield) as colorless oils.
8. All new compounds were fully characterized. Selected spectroscopic data for representative compounds. Compound 2: 1H
NMR (400 MHz, CDCl3): δ=0.82 (d, J=9.6 Hz, 1H), 1.36 (d, J=9.6 Hz, 1H), 2.23–2.27 (m, 1H), 2.23 (dd, J=1.5, 3.9 Hz,
1H), 2.47 (d, J=3.3 Hz, 1H), 2.52 (dd, J=1.5, 3.0 Hz, 1H), 2.61–2.68 (m, 1H), 2.89 (d, J=3.6 Hz, 1H), 3.13–3.18 (m, 1H),
3.15 (dd, J=1.0, 3.9 Hz, 1H), 5.55 (ddd, J=2.2, 4.3, 8.0 Hz, 1H), 5.63 (ddd, J=2.2, 4.3, 8.0 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ=29.0 (t), 31.3 (t), 38.4 (d), 40.0 (d), 41.8 (d), 49.2 (d), 50.9 (d), 53.2 (d), 129.5 (d), 132.1 (d). Compound 3: 1H
NMR (400 MHz, CDCl3): δ=1.33 (ddd, J=2.7, 3.3, 14.9 Hz, 1H), 1.33 (dd, J=7.8 Hz, 1H), 1.49 (dt, J=1.8, 8.2 Hz, 1H),
1.89 (dd, J=9.0, 14.9 Hz, 1H), 2.49–2.56 (m, 1H), 2.78 (br.s, 1H), 2.80 (dd, J=4.0, 8.0 Hz, 1H), 2.91 (br.s, 1H), 3.15 (d,
J=2.5 Hz, 1H), 3.30 (t, J=2.5 Hz, 1H), 6.06 (dd, J=2.9, 5.7 Hz, 1H), 6.10 (dd, J=2.9, 5.7 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ=31.0 (t), 43.9 (d), 44.6 (d), 46.4 (d), 50.9 (d), 51.9 (t), 60.7 (d), 61.8 (d), 134.8 (d), 135.0 (d). Compound 12: 1H
NMR (400 MHz, CDCl3): δ=0.94 (s, 6H), 1.32 (s, 6H), 1.56 (s, 6H); 13C NMR (100 MHz, CDCl3): δ=8.1, 10.6, 11.1, 58.7,
1
75.1, 142.6. Compound 13: H NMR (400 MHz, CDCl3): δ=0.86 (s, 6H), 1.42 (s, 12H); 13C NMR (100 MHz, CDCl3):
δ=6.7, 10.6, 64.6, 68.6.
9. Paulson, D. R.; Murray, A. S.; Fornoret, E. J. J. Org. Chem. 1978, 43, 2010–2013.
10. (a) Nelson, G. L.; Kuo, C.-L. Synthesis 1975, 105–106. (b) Bakke, J. M.; Lundquist, M. Acta Chem. Scand. 1990, 44,
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11. Tinsley, S. W.; MacPeek, D. L. US Patent 3,238,227; Chem. Abstr. 1966, 64, 19557e.
12. Murray, R. W.; Pillay, M. L.; Jeyaraman, R. J. Org. Chem. 1988, 53, 3007–3011.
13. King, B. B.; Douglas, W. M.; Efraty, A. In Organic Syntheses, Coll. Vol. 6; Noland, W. E., Ed.; John Wiley & Sons: New
York, 1988; p. 39.