IntroductionofC3-C4 Dou ble Bond into Eudesmane Skel e ton
J. Chin. Chem. Soc., Vol. 48, No. 2, 2001 263
+
(
4
M , 52%), 204 (32), 189 (28), 175 (14), 161 (58), 122 (60),
flashchromatography.Theproduct11 (278 mg, 92%) was
2
8
1 (100).
ob tained as white nee dle crys tals: mp 134-136 C; [ ]
51.2 (c 1.66, CHCl ); IR: 3286 (br), 1451, 1378, 1146, 912,
D
-
3
1 1
-
(
-)-3 -Chloro-4 H-eudesma-11,12-ene (9)
725, 704, 566 cm ; H NMR (CDCl
3
)
H
0.83 (3H, s, 10-Me),
To a mag net i cally stirred so lu tion of NCS (239 mg,
0.96 (3H, d,J = 6.0, 4-Me), 1.19 (6H, s, 11-Me), 4.33 (1H, br
+
1
.80 mmol) in THF (2.2 mL), a so lu tion of PPh
3
(472 mg, 1.8
d, J = 2.3, 3-H); EIMSm/z 243 (M -15, 1%), 225 (2), 200 (8),
mmol) in THF (1 mL) was added dropwise. The so lu tion was
stirredatroomtemperaturefor1h.Tothissuspension,asolu-
tion of the al co hol8 (350 mg, 1.58 mmol) in THF (3.5 mL)
was added and stir ring was con tin ued un til most of the solid
was dis solved into so lu tion (ca. 3 h). The re ac tion mix ture
was stripped of sol vent un der re duced pres sure and the res i-
due was treated with wa ter and ether. The or ganic layer was
185 (10), 164 (13), 149 (38), 59 (100). Anal. Calcd. for
15
C H27OCl: C, 69.61; H, 10.51. Found: C, 69.47; H, 10.32.
( )- -Eudesmol (3)
A sus pen sion of com pound11 (220 mg, 0.85 mmol),
LiBr (222 mg, 2.56 mmol) and Li CO (252 mg, 3.4 mmol) in
2
3
dry DMF (6 mL) was heated at 138-140 C for 5 h. Af ter it
was cooled, the so lu tion was di luted with ether and washed
with water and brine. After being dried over anhydrous
washed with wa ter, dried over an hy drous MgSO , fil tered
4
and evap o rated. The crude prod ucts were pu ri fied by flash
chromatography.Thecompound9 (334 mg, 88%) was ob-
MgSO
4
, the so lu tion was evap o rated to dry ness in vacuum.
2
6
tained as col or less oil: [ ]
1
0
D
-68.8 (c 3.9, CHCl
450, 886 cm ; H NMR (CDCl 0.85 (s, 3H, 10-Me),
.94 (d, 3H, J = 6.5 Hz, 4-Me), 1.73 (br s, 3H, 10-Me), 4.33
3
); IR: 1879,
Purificationbyflashchromatographygavepure 3 (170 mg,
90%): [ ]
-
1
1
23
9b
3
)
H
D
3 D
+27 (c 0.59, CHCl ), mp 74-76 C, (lit [ ]
+28.5 (c 1.2), mp 75 C); IR: 3302, 2939, 1453, 1376, 1144,
797 cm ; H NMR (CDCl ) 5.33 (1H, br s, 3-H), 1.62 (3H,
3 H
-
1 1
(
br q, 1H,J = 2.7 Hz, 3-H), 4.68 (br d, 1H,J = 1.42 Hz, 13-H),
+
4
1
7
.69 (br s, 1H, 13-H); EIMS m/z 240 (M , 64%), 225 (15),
s, 4-Me), 1.21 (6H, s, 11-Me), 0.77 (3H, s, 10-Me); EIMS m/z
222 (M , 9%), 204 (34), 149 (57), 107 (21), 93 (24), 91 (24),
59 (100).
+
97 (89), 161 (44), 81 (100); Anal. Calcd. for C15
4.81; H, 10.46. Found: C, 74.67; H, 10.16.
H
25Cl: C,
3
-Chloro-4 H-11,12-oxidoeudesma (10)
(+)-3 ,4 -Epoxy-eudesma-11-ol (12)
To a so lu tion of the com pound9 (325 mg, 1.35 mmol)
in CH Cl (40 mL) was addedm-CPBA (70%, 400 mg) un der
Asuspensionof(+)- -eudesmol 3 (90 mg, 0.41 mmol),
2
2
m-CPBA (120 mg) and NaHCO
3
(168 mg) in CH
2
2
Cl (6 mL)
stir ring at room tem per a ture. The mix ture was stirred at r.t.
for 40 min. Then the re ac tion mix ture was washed with 5%
aqueousKOHsolution,waterandbrinesuccessively.After
was stirred at 0 C for 30 min. Af ter the usual workup, the
crudeproductswerepurifiedbyflashchromatography,toaf-
1
8
ford the prod uct 12 (79 mg, 82%) as col or less oil: [ ]
+19.4 (c 0.9, CHCl ); IR: 3426 (br), 1453, 1381, 1166, 880
cm ; H NMR (CDCl 0.80 (3H, s, 10-Me), 1.23 (6H, s,
D
be ing dried over an hy drous MgSO
4
, the so lu tion was evap o-
3
-
1
1
rated to dry nessin vacuo. The crude prod ucts were pu ri fied
3
)
H
byflashchromatography. Thecompound10 (329 mg, 94%)
11-Me), 1.27 (3H, s, 3-Me), 2.96 (1H, br s, 3-H); EIMS m/z
1
+
wasobtainedascolorlessoil; H NMR (CDCl
3
)
H
0.84 (3H,
238 (M , 9%), 220 (49), 205 (66), 177 (10), 123 (100); Anal.
s, 10-Me), 0.94 (3H, d, J = 6.1, 4-Me), 1.27 (3H, s, 11-Me),
Calcd. for C15
10.68.
H
26
O : C, 75.58; H, 10.99. Found: C, 75.31; H,
2
2
3
.59 (2H, dd, J = 7.9 and 5.1, 13-H), 4.32 (1H, br d, J = 2.5,
-H); IR: 1450, 1380, 1305, 1234, 846, 813, 706, 581, 512
-
1
+
cm ; EIMS m/z 256 (M , 53%), 241 (19), 209 (11), 189 (13),
47 (12), 121 (21), 111 (63), 98 (100), 59 (89); Anal. Calcd.
25OCl: C, 70.15; H, 9.81. Found: C, 69.88; H, 9.62.
(+)-Chrysanthemol (1)
Method A: To a so lu tion of al co hol 12 (40 mg, 0.17
mmol) and Bu NI (96 mg, 0.26 mmol) in CHCl (3 mL) was
added dropwise a so lu tionof BF Et O (0.04 mL, 46.8-
47.8%,0.31mmol)inCHCl (3 mL) at 0 C.Thesolutionwas
1
for C 15
H
4
3
3
2
(-)-3 -Chloro-4 H-eudesma-11-ol (11)
3
To a well stirred so lu tion of LiAlH
4
(112 mg, 2.95
stirred for 10 min. Then the so lu tion was di luted with ether
(15 mL) and washed with wa ter, 5% a.q. NaOH, sat. a.q.
mmol) in dry ether (20 mL), was added slowly a so lu tion of
the epoxide 10 (300 mg, 1.16 mmol) in dry ether (40 mL) at
NaHCO
3
, brine and dried over an hy drous MgSO . Af ter the
4
-
15 C, un der ar gon. Then the tem per a ture was al lowed to
solvent was removed, the residue was purified by flash
raise to r.t. and the so lu tion was stirred for 10 h. The re ac tion
was quenched with 10% aque ous NaOH (0.5 mL) at 0 C. Af-
ter the usual workup, the crude prod ucts were pu ri fied by
chromatogrphy. The ti tle com pound 1 (20 mg, 50%) was ob-
2
3
tained as white nee dle crys tals. [ ]
D
+5.6 (c 0.72, CHCl
3
),
3
19
mp 144-146 C, (lit [ ]
D
+5.8 (c 0.51, CHCl ), mp 146-148
3