Coronanes
J . Org. Chem., Vol. 66, No. 7, 2001 2195
0.62 (m, 4H), 0.26-0.29 (m, 2H), -0.05-0.18 (m, 10H), -0.23-
(-)0.19 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 166.1, 135.0,
129.9, 69.5, 22.1, 21.6, 21.1, 20.3, 18.9, 10.5, 9.0, 6.3; MS (CI)
m/z 393 (M + H)+. HRMS (CI) calcd for C25H29O4: (M + H)+
393.2066, found: (M + H)+ 393.2066; Anal. Calcd. for
) 293 K; clear platy needles, 0.63 × 0.43 × 0.07 mm, 4598
independent measured reflections; refinement based on F2 to
give R1 ) 0.046, wR2 ) 0.116 for 3961 independent observed
reflections [|Fo| > 4σ(|Fo|), 2θ e 128°] and 686 parameters. The
absolute structure was assigned by internal reference to the
known chirality of the pentacyclopropyl chain.
C
25H28O4: C, 76.50; H, 7.19. Found: C, 76.36; H, 7.28; Crystal
data for 23: C25H28O4, M ) 392.5, monoclinic, P21 (no. 4), a )
Cor on a n e 36. Compound 36 was obtained from 35 (80 mg,
284.4 µmol) in CH2Cl2 (80 mL), 4 (15 mg, 56.8 µmol) and
pyridine (92 µL, 1.14 mmol) in CH2Cl2 (20 mL) as described
for 34 and was purified by chromatography (CH2Cl2:MeOH 30:
1) to give 36 (19 mg, 71%) as a white solid: mp 141-142 °C
9.852(1), b ) 10.659(1), c ) 10.526(1) Å, â ) 98.77(1)o, V )
1092.4(2) Å3, Z ) 2, Dc ) 1.193 g cm-3, µ(Cu-KR) ) 6.37 cm-1
,
F(000) ) 420, T ) 293 K; clear hexagonal plates, 0.93 × 0.33
× 0.30 mm, 1920 independent measured reflections; refine-
ment based on F2 to give R1 ) 0.055, wR2 ) 0.148 for 1821
independent observed reflections [|Fo| > 4σ(|Fo|), 2θ e 128°]
and 263 parameters. The absolute structure was assigned by
internal reference to the known chirality of the pentacyclo-
propyl chain.
(hexanes); Rf 0.29 (CH2Cl2:MeOH 30:1); [R]25 ) -3.5 (c 0.38,
D
CHCl3); IR (film) 1727 cm-1; 1H NMR (300 MHz, CDCl3) δ 9.02
(d, 2H, J ) 4.9 Hz), 8.45 (s, 2H), 7.99 (d, 2H, J ) 4.9 Hz), 4.83
(dd, 2H, J ) 4.7, 11.4 Hz), 3.65 (t, 2H, J ) 10.7 Hz), 1.16 (m,
2H), 0.68 (m, 2H), 0.14-0.54 (m, 14H) 0.07 (m, 2H); 13C NMR
(75 MHz, CDCl3) δ 165.1, 157.5, 151.2, 139.2, 123.0, 121.4,
70.4, 20.9, 20.8, 20.5, 20.4, 17.4, 9.4, 9.3, 9.0; MS (CI) m/z 471
(M + H)+; HRMS (CI) calculated for C29H31N2O4: (M + H)+
Cor on a n e 27. Macrolactone 27 was obtained as a colorless
oil from diester 26 in 70% yield (44 mg) as described for 22:
Rf 0.63 (hexanes: EtOAc 4:1); [R]25 ) -44.1 (c 2.2, CHCl3);
D
IR (film) 1724 cm-1; 1H NMR (300 MHz, CDCl3) δ 8.28 (s, 2H),
7.94-7.97 (m, 2H), 7.61-7.66 (m, 2H), 4.88 (dd, 2H, J ) 5.0,
11.3 Hz), 3.62 (dd, 2H, J ) 9.7, 11.3 Hz), 1.25-1.34 (m, 2H),
0.52-0.62 (m, 4H), 0.30-0.49 (m, 12H), 0.19-0.27 (m, 10H);
13C NMR (75 MHz, CDCl3) δ 167.9, 133.4, 130.2, 129.1, 128.6,
128.5, 70.0, 22.2, 21.7, 21.7, 20.0, 17.3, 10.8, 10.6, 10.0, 9.4;
MS (CI) m/z 523 (M + H)+; HRMS (CI) calcd for C35H39O4: (M
+ H)+ 523.2848, found: (M + H)+ 523.2846. Anal. Calcd for
471.2284 found: (M
29H30N2O4: C, 74.02; H, 6.43; N, 5.95. Found: C, 73.99; H,
+
H)+ 471.2285. Anal. Calcd for
C
6.46; N, 5.97; Crystal data for 36: C29H30N2O4, M ) 470.6,
tetragonal, P43 (no. 78), a ) b ) 11.006(1), c ) 41.345(2) Å, V
) 5008.5(3) Å3, Z ) 8 (there are two crystallographically
independent molecules in the asymmetric unit), Dc ) 1.248 g
cm-3, µ(Cu-KR) ) 6.69 cm-1, F(000) ) 2000, T ) 293 K; clear
needles, 0.53 × 0.30 × 0.30 mm, 4216 independent measured
reflections; refinement based on F2 to give R1 ) 0.043, wR2 )
0.107 for 3611 independent observed reflections [|Fo| > 4σ(|Fo|),
2θ e 128°] and 632 parameters. The absolute structure was
assigned by internal reference to the known chirality of the
pentacyclopropyl chain.
C
35H38O4: C, 80.43; H, 7.33. Found: C, 80.27; H, 7.30.
Cor on a n e 32. Compound 32 was obtained as white crystals
from 31 in 90% yield (45.7 mg) as described for 22 after
chromatography (hexanes: EtOAc 5:1): mp 146-149 °C (Et2O);
Rf 0.63 (hexanes: EtOAc 5:1); IR (CHCl3) 1712 cm-1; 1H NMR
(400 MHz, CDCl3) δ 7.97 (d, 4H, J ) 8.3 Hz), 7.23 (d, 4H, J )
8.2 Hz), 4.80 (dd, 2H, J ) 4.3, 11.3 Hz), 4.09 (s, 2H), 3.44 (t,
2H, J ) 11.0 Hz), 0.96-1.05 (m, 2H), 0.82-0.89 (m, 2H), 0.46-
0.52 (m, 2H), 0.36-0.44 (m, 4H), 0.32-0.35 (m, 2H), 0.03-
0.12 (m, 4H), -0.03-0.02 (m, 2H), -0.24 (t, 2H, J ) 6.9 Hz);
13C NMR (100 MHz, CDCl3) δ 166.4, 146.3, 130.0, 128.9, 128.8,
68.5, 41.9, 20.7, 19.6, 18.9, 17.8, 17.7, 9.4, 9.1, 7.7; MS (CI)
m/z 500 (M + NH4)+, 483 (M + H)+; HRMS (CI) calcd for
(1R,3S,4R,6S,7R,9S,10R,12S,13R,15S)-1-[(ter t-Bu tyld i-
m eth ylsilyloxy)m eth yl]-15-eth en yl-qu in qu ecyclopr opan e
(37). Dess-Martin reagent (116 mg, 0.274 mmol) was added
to a mixture of 6 (86 mg, 0.228 mmol) and pyridine (37 µL,
0.556 mmol) in CH2Cl2 (3 mL). After stirring for 1.5 h, a
mixture of saturated aqueous NaHCO3 and Na2S2O3 was added
at 0 °C, and the mixture was extracted with Et2O (20 mL).
The organic layer was washed with saturated aqueous NH4Cl
and brine, dried (Na2SO4), and concentrated in vacuo. Chro-
matography (hexanes:Et2O 95:5) gave the corresponding al-
dehyde which was dissolved in THF (2 mL) and added to a
solution of methylenetriphenylphosphorane [prepared in situ
from methyltriphenylphosphonium bromide (135 mg, 0.378
mmol) and t-BuOK in THF (1M; 0.4 mL, 0.4 mmol)] in THF
(5 mL) at 0 °C. After stirring for 1 h at room temperature,
saturated aqueous NH4Cl was added, the mixture was ex-
tracted with Et2O, dried (Na2SO4), and evaporated in vacuo.
Chromatography (hexanes:Et2O 97:3) gave 37 (74 mg, 87%)
C
32H35O4: (M + H)+ 483.2535, found (M + H)+ 483.2541. Anal.
Calcd for C32H34O4: C, 79.63; H, 7.11. Found: C, 79.86; H,
7.03; Crystal data for 32: C32H34O4, M ) 482.6, monoclinic,
P21 (no. 4), a ) 5.655(1), b ) 12.154(2), c ) 19.727(2) Å, â )
90.46(1)°, V ) 1355.6(3) Å3, Z ) 2, Dc ) 1.182 g cm-3, µ(Cu-
KR) ) 6.07 cm-1, F(000) ) 516, T ) 293 K; clear blocks, 0.30
× 0.27 x 0.27 mm, 2344 independent measured reflections;
refinement based on F2 to give R1 ) 0.098, wR2 ) 0.271 for
1392 independent observed reflections [|Fo| > 4σ(|Fo|), 2θ e
127°] and 325 parameters. The absolute structure was as-
signed by internal reference to the known chirality of the
pentacyclopropyl chain.
as a colorless oil: Rf 0.55 (hexanes:EtOAc 20:1); [R]25
)
D
-164.1 (c 1.0, CHCl3); IR (film) 1636, 1254, 1089, 837 cm-1
;
Cor on a n e 34. Diol 4 (16.1 mg, 61.6 µmol) and pyridine (13.3
µL, 163.8 µmol) in dry CH2Cl2 (20 mL) were added dropwise
with stirring to chloride 33 (25 mg, 81.9 µmol) in dry CH2Cl2
(60 mL). After 24 h, the solvent was removed under reduced
pressure, and the product was purified by chromatography
(CH2Cl2:MeOH 90:1) to give 34 (18.7 mg, 62%) as a white
solid: mp 116-118 °C (hexanes and CH2Cl2); Rf 0.25 (CH2Cl2:
1H NMR (300 MHz, CDCl3) δ 5.31-5.43 (m, 1H), 5.00 (dd, 1H,
J ) 1.7, 17.0 Hz), 4.82 (dd, 1H, J ) 1.7, 10.2 Hz), 3.39-3.48
(m, 2H), 1.13-1.18 (m, 1H), 0.91 (s, 9H), 0.83-0.87 (m, 1H),
0.64-0.75 (m, 2H), 0.42-0.60 (m, 8H), 0.18-0.29 (m, 2H), 0.06
(s, 6H), 0.04-0.13 (m, 6H); 13C NMR (75 MHz, CDCl3) δ 141.9,
111.1, 66.7, 30.3, 26.0, 22.3, 21.3, 19.6, 18.6, 18.5, 18.4, 18.3,
18.2, 18.1, 11.8, 8.3, 8.2, 8.1, 7.8, -5.1; MS (CI) m/z 390 (M +
NH4)+; HRMS (CI) calculated for C24H44NOSi: (M + NH4)+
MeOH 90:1); [R]25D ) +54 (c 1.41, CHCl3); IR (film) 1715 cm-1
;
UV-vis (CHCl3:MeOH 3:1) λmax (log ꢀ): 242.7 (2.03), 249.9
390.3192 found: (M + NH4)+ 390.3192. Anal. Calcd for C24H40
-
1
(1.73), 281.7 (1.56) nm; H NMR (300 MHz, CDCl3) δ 8.45 (s,
OSi: C, 77.36; H, 10.83. Found: C, 77.14; H, 10.84.
4H), 7.97 (s, 2H), 4.54 (dd, 2H, J ) 7.7, 11.2 Hz), 4.20 (dd, 2H,
J ) 6.2, 11.2 Hz), 1.42 (m, 2H), 0.78 (m, 2H), 0.68 (m, 2H),
0.32-0.57 (m, 10H) 0.03-0.15 (m, 4H); 13C NMR (75 MHz,
CDCl3) δ 166.1, 149.1, 145.6, 137.3, 130.5, 128.2, 123.9, 70.3,
22.8, 21.8, 21.5, 19.1, 17.5, 11.3, 10.3, 9.9; MS (EI) m/z 494
(M+•); HRMS (EI) calculated for C31H30N2O4: (M+•) 494.2205
found: (M+•) 494.2193. Anal. Calcd for C31H30N2O4: C, 75.28;
H, 6.11; N, 5.66. Found: C, 75.06; H, 6.15; N, 5.51; Crystal
data for 34: C31H30N2O4 ‚ H2O, M ) 512.6, monoclinic, P21
(no. 4), a ) 7.034(1), b ) 35.773(2), c ) 11.172(1) Å, â )
104.13(1)o, V ) 2725.9(2) Å3, Z ) 4 (there are two crystallo-
graphically independent molecules in the asymmetric unit),
Dc ) 1.249 g cm-3, µ(Cu-KR) ) 6.86 cm-1, F(000) ) 1088, T
(1R,3S,4R,6S,7R,9S,10R,12S,13R,15S)-15-Eth en yl-1-qu in -
qu ecyclop r op a n em eth a n ol (38). Bu4NF in THF (1M; 1.288
mL, 1.288 mmol) was added to quinquecyclopropane 37 (240
mg, 644 µmol) in THF (5 mL). The mixture was stirred at room
temperature for 1 h when Et2O (5 mL) and saturated aqueous
NH4Cl (3 mL) were added. The mixture was stirred for a
further 5 min, and 1 N HCl (5 mL) was added, and the layers
were separated. The aqueous layer was extracted with Et2O
(3 × 10 mL), and the combined organic extracts were dried
(MgSO4) and concentrated in vacuo. Chromatography (hex-
anes:EtOAc 3:1) gave alcohol 38 (0.164 g, 97%) as colorless
crystals: mp 38 °C (hexanes and Et2O); Rf 0.38 (hexanes:
1
EtOAc 3:1); IR (CHCl3) 1633, 1032, 928, 897 cm-1; H NMR