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HETEROCYCLES, Vol. 71, No. 8, 2007
12. Electron-withdrawing or bulky groups attached to the α-positions of ketone, in addition to
accelerating the reaction, usually increase the amount of oxide formed. C. D. Gutsche, Org.
Reactions; Wiley and Sons: New York, 1954; Vol. 8, pp. 364-429.
13. Compound 5: 1H NMR (400MHz, D2O + DCl): δ 1.69-1.75 (m, 1H, H-4’), 1.90 (q, J = 12.7 Hz, 1H,
H-2a), 1.99-2.06 (m, 2H, H-4’, H-3’’’a), 2.08-2.16 (m, 2H, H-3’), 2.24 (ddt, J = 14.4, 7.3, 3.9 Hz,
1H, H-3’’’b), 2.39 (dt, J = 12.9, 4.6 Hz, 1H, H-2b), 3.20-3.24 (m, 1H, H-6’a), 3.24 (t, J = 7.4 Hz, 2H,
H-4’’’) 3.35 (dd, J = 13.6, 3.4 Hz, 1H, H-6’b), 3.44 (t, J = 10.5 Hz, 1H, H-3’’), 3.50 (s, 3H, H-8),
3.63-3.68 (m, 1H, H-2’), 3.77 (t, J = 10.0 Hz, 1H, H-4’’), 3.82 (d, J = 10.7 Hz, 1H, H-7a), 3.86 (dd,
J = 10.0, 3.7 Hz, 1H, H-2’’), 3.87 (d, J = 2.9 Hz, 2H, H-6’’), 3.87-3.92 (m, 1H, H-3), 3.94 (d, J =
10.8 Hz, 1H, H-7b), 4.02 (d, J = 10.7 Hz, 1H, H-6), 4.06 (dt, J = 10.0, 2.9 Hz, 1H, H-5’’), 4.12 (d, J
= 11.0 Hz, 1H, H-4), 4.23-4.29 (m, 1H, H-5’’), 4.33 (dd, J = 9.0, 3.6 Hz, 1H, H-2’’’), 4.35-4.40 (m,
1H, H-1), 5.19 (d, J = 3.6 Hz, 1H, H-1’’), 5.76 (d, J = 3.2 Hz, 1H, H-1’); 13C NMR (100MHz, D2O +
DCl): δ 21.5 (C-3’), 26.0 (C-4’), 31.2 (C-2), 31.7 (C-11), 37.9 (C-12), 43.3 (C-6’), 48.4 (C-1), 48.9
(C-3), 49.9 (C-2’), 56.3 (C-3’’), 60.0 (C-8), 60.6 (C-6’’), 66.4 (C-4’’), 67.2 (C-5’), 69.0 (C-2’’), 70.5
(C-10), 71.1 (C-7), 73.5 (C-5’’), 77.7 (C-5), 81.8 (C-4), 84.0 (C-6), 96.6 (C-1’), 100.4 (C-1’’), 176.4
1
(C-9). Compound 6: H NMR (400MHz, D2O + ND3): δ 1.32-1.50 (m, 2H, H-2a, H-4’a), 1.65-1.80
(m, 4H, H-3’, H-4’b, H-3’’’a), 1.85-1.95 (m, 1H, H-3’’’b), 1.97-2.05 (m, 1H, H-2b), 2.60-2.70 (m,
2H, H-6’), 2.70-2.80 (m, 2H, H-4’’’), 2.85-2.92 (m, 1H, H-2’), 2.98 (t, J = 10.0 Hz, 1H, H-3’’),
3.15-3.25 (m, 1H, H-3), 3.32 (t, J = 10.0 Hz, 1H, H-4’’), 3.39 (dd, J = 10.5, 3.9 Hz, 1H, H-2’’), 3.45
(d, J = 10.3 Hz, 1H, H-4), 3.76-3.78 (m, 2H, H-6’’), 3.81 (d, J = 10.7 Hz, 1H, H-6), 3.85-3.94 (m,
1H, H-5’), 3.90 (d, J = 11.7 Hz, 1H, H-7a), 3.99 (d, J = 11.7 Hz, 1H, H-7b), 3.99-4.05 (m, 1H,
H-5’’), 4.18 (dd, J = 9.2, 3.6 Hz, 1H, H-2’’’), 4.32-4.40 (m, 1H, H-1), 5.05 (d, J = 3.9 Hz, 1H, H-1’’),
1
5.11 (d, J = 3.2 Hz, 1H, H-1’). Compound 7: H NMR (400MHz, D2O + ND3): δ 1.36 (q, J = 12.5
Hz, 1H, H-2a), 1.42-1.52 (m, 1H, H-4’a), 1.66-1.81 (m, 4H, H-3’, H-4’b, H-3’’’a), 1.87-1.96 (m, 1H,
H-3’’’b), 2.02 (dt, J = 13.2, 4.6 Hz, 1H, H-2b), 2.60 (s, 6H, H-8, H-9), 2.63-2.70 (m, 2H, H-6’),
2.73-2.82 (m, 2H, H-4’’’), 2.97 (t, J = 9.8 Hz, 1H, H-3’’), 3.02 (d, J = 14.4 Hz, 1H, H-7a), 3.03-3.10
(m, 2H, H-3, H-2’), 3.15 (d, J = 14.2 Hz, 1H, H-7b), 3.33 (t, J = 9.7 Hz, 1H, H-4’’), 3.40 (d, J = 10.5
Hz, 1H, H-2’’), 3.41 (d, J = 10.5 Hz, 1H, H-4), 3.75-3.82 (m, 3H, H-6, H-6’’), 3.90-3.98 (m, 2H,
H-1, H-5’), 4.00-4.04 (m, 1H, H-5’’), 4.18 (dd, J = 9.5, 3.6 Hz, 1H, H-2’’’), 5.05 (s, 1H, H-1’ or
H-1’’), 5.06 (s, 1H, H-1’ or H-1’’). Compound 10: 1H NMR (400MHz, D2O + ND3): δ 1.40-1.54 (m,
1H, H-4’a), 1.60-1.88 (m, 6H, H-2, H-3’, H-4’b, H-3’’’a), 1.96-2.05 (m, 1H, H-3’’’b), 2.46 (t, J =
11.9 Hz, 1H, H-6a), 2.71 (dd, J = 13.4, 7.8 Hz, 1H, H-6’a), 2.79 (dd, J = 13.4, 3.9 Hz, 1H, H-6’b),
2.82-2.92 (m, 3H, H-2’, H-4’’’), 3.04 (t, J = 9.8 Hz, 1H, H-3’’), 3.34-3.38 (m, 1H, H-6b), 3.38 (t, J =
9.8 Hz, 1H, H-4’’), 3.42-3.45 (m, 1H, H-3), 3.46 (dd, J = 10.2, 3.9 Hz, 1H, H-2’’), 3.81-3.94 (m, 4H,