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The Journal of Organic Chemistry
and 4-dimethylaminepyridine (8.3 mg, 0.068 mmol) were
ACKNOWLEDGMENT
1
2
3
4
5
6
7
8
dissolved in anhydrous dichloromethane. Then Et3N (94 μL,
0.68 mmol) was added. The resulting mixture was stirred at
room temperature and monitored by TLC. After completion of
the reaction, it was washed with water and dried with sodium
sulfate. The organic solvent was evaporated under reduced
pressure and purified on silica gel column with petroleum
ether, dichloromethane and ethyl acetate (70:70:1) as eluent.
The earlier eluting fractions gave diastereomer 23A (83.8 mg,
44 %) while the later parts gave diastereomer 23B (83.9 mg,
44 %). Yellow solid; 12 h; yield 44% (83.8 mg); Rf = 0.3
(PE/EA 50 : 1); 1H NMR (400 MHz, CDCl3) δ 8.03–7.94 (m, 5H),
7.91–7.89 (m, 3H), 7.86 (d, J = 8.8 Hz, 1H), 7.82 (d, J = 7.6 Hz,
1H), 7.56 (d, J = 8.4 Hz, 1H), 7.42 (d, J = 2.0 Hz, 1H), 7.27–7.22
(m, 2H), 6.72 (t, J = 8.4 Hz, 1H), 3.35 (d, J = 15.2 Hz, 1H), 2.69
(d, J = 15.6 Hz, 1H), 2.32–2.23 (m, 2H), 2.04–2.00 (m, 2H), 1.88
(d, J = 18.4 Hz, 1H), 1.42–1.38 (m, 1H), 1.26–1.22 (m, 1H), 0.98
(s, 3H), 0.71 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 213.5,
146.6, 133.2, 132.0, 131.7, 131.6, 131.0, 130.4, 129.5, 129.4,
128.1, 127.8, 127.7, 127.6, 127.3, 127.2, 127.0, 126.1, 126.0,
124.9, 124.0, 120.6, 119.9, 57.8, 47.8, 46.6, 42.6, 42.4, 26.9,
24.7, 20.0, 19.6. HRMS (ESI-TOF) m/z [M + H]+ calcd. for
C36H31O4S 559.1938, found 559.1939.
We thank the National Natural Science Foundation of China
(21672196, 21404096, 21602001, U1463202) for financial
support.
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Hexahelicen-11-yl((1S,4R)-7,7-dimethyl-2-
oxobicyclo[2.2.1]heptan-1-yl)methanesulfonate (23B): Yellow
1
solid; 12 h; yield 44% (83.9 mg); Rf = 0.3 (PE/EA 50 : 1); H
NMR (400 MHz, CDCl3) δ 8.03–7.90 (m, 8H), 7.86 (d, J = 8.8 Hz,
1H), 7.82 (d, J = 8.0 Hz, 1H), 7.55 (d, J = 8.4 Hz, 1H), 7.44 (d, J =
2.0 Hz, 1H), 7.28–7.24 (m, 2H), 6.72 (t, J = 8.0 Hz, 1H), 3.29 (d,
J = 15.2 Hz, 1H), 2.71 (d, J = 15.2 Hz, 1H), 2.35–2.29 (m, 1H),
2.11–1.98 (m, 3H), 1.91 (d, J = 18.8 Hz, 1H), 1.54–1.47 (m, 1H),
1.44–1.38 (m, 1H), 0.78 (s, 3H), 0.71 (s, 3H). 13C{1H} NMR (100
MHz, CDCl3) δ 213.8, 146.6, 133.2, 132.0, 131.6, 130.9, 130.4,
129.5, 129.4, 128.2, 127.9, 127.7, 127.5, 127.3, 127.2, 127.0,
126.2, 126.0, 124.9, 123.9, 120.4, 119.8, 57.8, 47.8, 46.9, 42.8,
42.4, 26.9, 24.6, 19.7, 19.6. HRMS (ESI-TOF) m/z [M + H]+
calcd. for C36H31O4S 559.1938, found 559.1939.
M-(-)-2-Hexahelicenol ((M)-(-)-21): 14p 23A and KOH (85%)
(99 mg, 1.5 mmol) were dissolved in THF/MeOH (1:1, v/v, 30
mL). The resulting mixture was refluxed at 80 oC for 10 hours.
When the reaction finished, it was cooled to room tempera-
ture and poured into ice water. Then it was quenched with 1.0
M HCl and extracted with dichloromethane. Dried with sodi-
um sulfate and the solvent was removed under reduced pres-
sure. The crude product was purified on silica gel column with
petroleum ether and ethyl acetate to give the product (M)-(-)-
21/(P)-(+)-21.Yellow solid; 9 h; yield 99% (63.4 mg); [α]D = -
3282 (c 0.08, CHCl3).
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AUTHOR INFORMATION
Notes
The authors declare no competing financial interest.
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