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D.L. Chen, F.P. Wang / Chinese Chemical Letters 23 (2012) 1378–1380
2 steps. Using trifluoroacetic acid, was the MOM group removed to give phenol precursor 11 in 85% yield. With
phenol 11 in hand, we next explored the key oxidative dearomatization/intramolecular Diels–Alder reaction. Since a
significant amount of undesired intermolecular dimerization product was produced using the literature procedure [11],
we slightly modified the procedure as follows: the precursor 11 was oxidized with PhI(OAc)2 using methanol as
solvent in an ice-water bath, after 30 min switching the solvent from methanol to xylene, the resulting masked ortho-
quinone 12 was heated at 160 8C to provide the lactone 13 [12] in 67% yield. Compound 13 was assigned as the desired
endo product of the Diels–Alder reaction due to the critical correlation between H-9 and the methoxyl of C-15 in the
NOESY spectrum of the hydrogenation product 14 [13]. Finally, the lactone 7 [14] was yielded from ketone 14
through a Wittig methylenation.
In conclusion, an efficient construction of highly functionalized C/D rings of atisine-type C20-diterpenoid alkaloids
has been successfully accomplished within 6 steps from a know aromatic aldehyde 8, using oxidative dearomatization/
intramolecular Diels–Alder reaction, which demonstrate a convergent strategy to construct highly functionalized
bicyclo[2.2.2]octane systems by Liao and co-worker. Further elaboration into the A-, B-, E-rings base on the lactonic
ring of compound 7 are under investigated in our laboratory and will be published in due course.
Acknowledgment
We are grateful for the financial support provided by the National Science Foundation of China (No. 81273387).
References
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[12] Spectra data of compound 13: IR (KBr, cmÀ1): 2978, 2911, 1776, 1738, 1466, 1053, 986; 1H NMR (400 MHz, CDCl3): d 1.78–1.84 (m, 1H),
2.22–2.29 (m, 1H), 3.16 (s, 3H), 3.20 (t, 1H, J = 2.8 Hz), 3.41 (dd, 1H, J = 6.8, 10.4 Hz), 3.50 (s, 3H), 4.50 (d, 1H, J = 8.8 Hz), 4.69 (d, 1H,
J = 8.4 Hz), 6.21 (d, 1H, J = 8.4 Hz), 6.53 (t, 1H, J = 7.6 Hz); 13C NMR (100 MHz, CDCl3): d 24.9 (CH2), 39.8 (CH), 47.8 (CH), 50.3 (CH3),
51.5 (CH3), 53.7 (C), 69.6 (CH2), 93.7 (C), 132.7(CH), 133.8 (CH), 175.0 (C), 201.7 (C); HR-ESIMS: m/z: C12H14O5 [M+Na]+ 261.0738
(calcd. 261.0739).
[13] Spectra data of compound 14: IR (KBr, cmÀ1): 2950, 2987, 1782, 1739, 1370, 1065, 976; 1H NMR (400 MHz, CDCl3): d 1.78–1.91 (m, 5H),
2.16 (dt, 1H, J = 2.0, 4.4 Hz), 2.42 (s, 1H), 3.14 (t, 1H, J = 10.0 Hz), 3.18 (s, 3H), 3.57 (s, 3H), 3.95 (d, 1H, J = 8.4 Hz,), 4.59 (d, 1H,
J = 8.8 Hz,); 13C NMR (100 MHz, CDCl3): d 21.2 (CH2), 21.9 (CH2), 22.8 (CH2), 39.5 (CH), 42.4 (CH), 48.1 (C), 51.0 (CH3), 51.9 (CH3), 70.2
(CH2), 96.9 (C), 175.8 (C), 208.0 (C); HR-ESIMS: m/z: C12H16O5 [M+Na]+ 263.0890 (calcd. 263.0895).
[14] Spectra data of compound 7: IR (KBr, cmÀ1): 2924, 1648, 1514, 1104; 1H NMR (400 MHz, CDCl3): d 1.61–1.72 (m, 4H), 1.83–1.95 (m, 2H),
2.47 (d, 1H, J = 2.8 Hz), 3.10–3.13 (m, 1H), 3.16 (s, 3H), 3.38 (s, 3H), 3.96 (d, 1H, J = 8.4 Hz), 4.60 (d, 1H, J = 8.4 Hz), 5.21 (s, 1H), 5.22 (s,
1H); 13C NMR (100 MHz, CDCl3): d 21.7 (CH2), 25.2(CH2), 26.4 (CH2), 38.2 (CH), 40.7 (CH), 47.9 (C), 50.0 (CH3), 50.6 (CH3), 71.2 (CH2),
+
100.0 (C), 113.3 (CH2), 148.9 (C), 177.4 (C); HR-ESIMS: m/z: C13H18O4 [M+Na] 261.1101 (calcd. 261.1103).