EXPERIMENTAL
13
PMR and C NMR spectra were taken in 10–20% solutions in deuterated solvent with solvent resonance or SiMe as
4
internal standard on Bruker AM-300 (300.13 and 75.47 MHz) and Avance III 500 (500.13 and 125.75 MHz) instruments.
Chemical shifts are given on the ꢄ-scale. IR spectra were recorded in a thin layer or nujol suspension on a Shimadzu instrument.
Elemental analysis was performed on a Euro EA 3000 analyzer. Optical rotation angles were measured on a PerkinElmer 341
polarimeter (ꢅ 589 nm) at 20°C.
The XSA was carried out on a Bruker Smart Apex2 CCD diffractometer at 100 K (ꢅ Mo Kꢃ-radiation, 2ꢆ
= 64°).
max
The dataset of measured intensities was processed using the SAINT and SADABS programs included in the Apex2 program
set [11]. The structure was solved by direct methods and refined by anisotropic full-matrix least-squares methods for non-
2
hydrogen atoms over F . All calculations were performed on an IBM PC using the SHELXTL program set [12].
hkl
The course of reactions was monitored by TLC on Sorbfil PTSKh-AF-Aplates. Compounds were detected by spraying
plates with H SO solution (5%) with subsequent heating to 100–120°C. The eluents were solvent systems CHCl :MeOH
2
4
3
(50:1, 10:1, 5:1). Column chromatography was carried out over standard silica gel 60 (0.063–0.2 mm, 70–230 mesh) (Macherey-
Nagel, Germany). Analytical data of all synthesized compounds agreed with those calculated.
Framework quinopimaric acid derivatives 1 and 2 were synthesized as before [13]. The physical and spectral
characteristics of 1 and 2 corresponded with the literature data.
3,7 4,11 5,10 8,12 15,20
Methyl (7S,8S,16R,20R)-16,20-Dimethyl-4-isopropyl-6-chloro-9-oxoheptacyclo[10.8.0.0 .0 .0 .0 .0
]
eicosane-16-carboxylate (3). C H ClO . Compound 1 (0.7 g, 1.7 mmol) in anhydrous Py (23 mL) at 0°C was stirred,
27 37
3
treated dropwise with POCl (1.1 mL, 12 mmol) and stirred at 0°C for 0.5 h and at room temperature for 7 h. The solvent was
3
distilled at reduced pressure. The residue was treated with CHCl (20 mL) and washed with HCl solution (1%) and H O. The
3
2
organic phase was dried over Na SO . The solvent was removed at reduced pressure to afford 3 (0.72 g, 99.9%), mp 114–
2
4
20
–1
118°C, [ꢃ] +66ꢂ (c 2.0; CHCl ). IR spectrum ( , cm ): 1726, 1460, 1377, 1244, 1194, 1142, 1103, 1053, 974, 754.
D
3
13
C NMR spectrum (CDCl + ÑD OD, ꢄ, ppm): 15.01 (q, Ìå), 16.25 (q, Ìå), 16.66 (q, Ìå), 16.85 (t, Ñ-18), 17.15 (t, Ñ-14),
3
3
18.25 (q, Ìå), 20.81 (t, Ñ-2), 26.31 (d, Ñ-21), 33.29 (t, Ñ-13), 34.17 (d, Ñ-10), 36.40 (s, Ñ-20), 37.27 (t, Ñ-17), 37.60 (t, Ñ-19),
38.33 (s, Ñ-12), 38.80 (d, Ñ-5), 41.45 (d, Ñ-7), 42.35 (d, Ñ-11), 44.83 (d, Ñ-3), 45.27 (d, Ñ-15), 46.86 (s, Ñ-16), 49.30
(d, Ñ-1), 50.61 (s, Ñ-4), 51.66 (q, ÑÎÎÌå), 56.95 (d, Ñ-6), 57.05 (d, Ñ-8), 179.15 (s, ÑÎÎ), 218.45 (s, Ñ=Î).
Methyl
[10.8.0.0 .0 .0 .0 .0
(16R,20R)-6-[(2-Chloroacetyl)oxy]-4-isopropyl-16,20-dimethyl-9-oxoheptacyclo
3,7 4,11 5,10 8,12 15,20
]eicosane-16-carboxylate (4). C H ClO . Methyl ester of 1 (1.0 g, 2.43 mmol) in
29 39 5-
anhydrous CHCl (20 mL) was treated with chloroacetyl chloride (1 mL) and refluxed for 15 h. The solvent was evaporated.
3
The residue was purified by column chromatography over silica gel using CHCl –MeOH (50:1). Yield 86%, mp 204–205ꢂÑ
3
20
–1
(CHCl ), [ꢃ] +73ꢂ (c 2.0; CHCl ). IR spectrum ( , cm ): 1738, 1721, 1462, 1375, 1275, 1254, 1165, 1140, 1103, 1028,
988, 785. C NMR spectrum (CDCl , ꢄ, ppm): 15.34 (q, Ìå), 16.64 (q, Ìå), 17.07 (q, Ìå), 17.21 (t, Ñ-18), 17.56 (t, Ñ-14),
3
D
3
13
3
18.57 (q, Ìå), 21.11 (t, Ñ-2), 26.62 (d, Ñ-21), 33.60 (t, Ñ-13), 35.01 (d, Ñ-10), 36.69 (t, Ñ-17), 37.57 (s, Ñ-20), 37.90 (t, Ñ-19),
38.37 (s, Ñ-12), 39.10 (d, Ñ-5), 40.36 (d, Ñ-7), 40.78 (t, CH Ñl), 42.55 (d, Ñ-11), 43.74 (d, Ñ-3), 45.41 (d, Ñ-15), 47.10
2
(s, Ñ-16), 49.57 (d, Ñ-1), 50.77 (s, Ñ-4), 51.94 (q, ÑÎÎÌå), 57.10 (d, Ñ-8), 77.13 (d, Ñ-6), 166.14 (s, ÎÑÎ), 178.99 (s, ÑÎÎ),
216.31 (s, Ñ=Î). A CIF file containing complete information on the structure was deposited in the CCDC (No. 948487) (http:/
/www.ccdc.cam.ac.uk/deposit).
( 7 S , 8 S , 1 6 R , 2 0 R ) - 6 - ( A c e t y l o x y ) - 4 - i s o p r o p y l - 1 6 , 2 0 - d i m e t h y l - 9 - o x o h e p t a c y c l o
3,7 4,11 5,10 8,12 15,20
[10.8.0.0 .0 .0 .0 .0
]eicosane-16-carboxylate (5). C H O . A mixture of 2 (1.3 g, 3.15 mmol) in Ac O
29 40 5 2
(6 mL) was refluxed for 1 h and evaporated to dryness. The residue was dissolved in CHCl (30 mL), washed with H O
3
2
(2 ꢇ 10 mL), and dried over Na SO . The solvent was removed at reduced pressure to afford the acetate (1.36 g), quantitative
2
4
20
–1
yield, mp 68–69°C, [ꢃ] +65ꢂ (c 2.1; CHCl ). IR spectrum ( , cm ): 1747, 1732, 1462, 1377, 1236, 1194, 1142, 1103, 1051,
752. C NMR spectrum (CDCl , ꢄ, ppm): 15.16 (q, Ìå), 16.30 (q, Ìå), 16.76 (q, Ìå), 16.81 (t, Ñ-18), 17.49 (t, Ñ-14), 18.41
D
3
13
3
(q, Ìå), 20.94 (q, ÌåÑÎ), 21.01 (t, Ñ-2), 26.43 (d, Ñ-21), 33.48 (t, Ñ-13), 34.86 (d, Ñ-10), 35.69 (s, Ñ-20), 37.37 (t, Ñ-17),
37.57 (t, Ñ-19), 38.24 (s, Ñ-12), 38.91 (d, Ñ-5), 40.36 (d, Ñ-7), 42.37 (d, Ñ-11), 43.64 (d, Ñ-3), 45.44 (d, Ñ-15), 47.94
(s, Ñ-16), 48.94 (d, Ñ-1), 50.53 (s, Ñ-4), 57.05 (d, Ñ-8), 75.02 (d, Ñ-6), 169.78 (s, ÑÎÌå), 174.00 (s, ÑÎÎ), 216.46
(s, Ñ=Î).
( 1 6 R , 2 0 R ) - 1 6 - ( 2 - D i a z o a c e t y l ) - 6 - ( a c e t y l o x y ) - 4 - i s o p r o p y l - 1 6 , 2 0 - d i m e t h y l - 9 -
3,7 4,11 5,10 8,12 15,20
oxoheptacyclo[10.8.0.0 .0 .0 .0 .0
]eicosane (7). C H N O . A suspension of 5 (0.55 g, 1.25 mmol) in
29 38 2 4
1037