DERIVATIVES OF L-PIMARIC ACID IN THE SYNTHESIS
1141
12.3), 3.98 d.d (1H, H17, J17B,1 4), 4.23 d.d (1H,
sulfonate, and the mixture was stirred at 40 C for
3 h. Then the reaction mixture was evaporated, and
the residue was subjected to chromatography (SiO2,
eluent hexane ethyl acetate, 1: 1). We obtained
0.38 g (80%) of compound V, [ ]2D0 5.0 (c 1.3,
11
H16, J16B,2 4), 5.21 s (1H, CHPh), 5.42 s (1H, H ),
_
7.26 7.45 m (5H, C6H5). 13C NMR spectrum
(
C, ppm): 16.13 (C18), 17.33 (C6), 17.78 (C19),
19.34 (C9), 20.49 (C15), 21.21 (C14), 29.67 (C4),
33.34 (C13), 35.30 (C7), 35.97 (C10), 36.92 (C3),
37.28 (C8), 38.04 (C4b), 38.68 (C5), 39.80 (C10a),
45.22 (C2), 48.13 (C8a), 53.19 (C1), 55.23 (C4a),
1
CHCl3). H NMR spectrum, , ppm (J, Hz): 0.55 s
(3H, C18H3), 0.73 s (3H, C19H3), 0.85 m (1H, H5),
0.97 d (3H, C14H3, 6.8), 0.98 d (3H, C15H3, 6.8),
1.07 m (1H, H4), 1.19 1.52 m (10H, H4a, H5,
C6H2, C7H2, H8a, C9H2, H10), 1.62 d.d.d (1H, H4,
12.6, 9.8, 2.8), 1.83 d.t (1H, H1, J1,2 = = J1,17B
10.5, J1,17A 2.2), 1.94 d.d (1H, H10, 9, 2), 2.14
2.20 m (2H, H2, H13), 2.31 m (1H, H3), 2.91 d (1H,
71.87 (C17), 72.28 (C16), 74.70 (C20), 107.40
11
_
(CHPh), 124.79 (C ), 126.00, 128.25, 128.46,
139.19 (C6H5), 147.55 (C12).
13 ,19 -5-Benzyloxymethyl-5,9-dimethyl-21-
isopropyl-16-phenyl-15, 17-dioxapentacyclo-
[10.7.2.01,10.04,9.013,19]heneicos-20-ene (IV). To a
solution of 4.6 g (10 mmol) of compound III in 5 ml
of dichloromethane was added 5 ml of 50% solution
of NaOH, 0.17 g (0.5 mmol) of tetrabutylammonium
hydrogen sulfate, and 7 ml (61 mmol) of benzyl
chloride. The reaction mixture was vigorously stirred
at 45 50 C for 5 h, then washed with water till
pH 7, the organic layer was separated, dried on
MgSO4, evaporated, and the residue was subjected to
chromatography (SiO2, eluent hexane ethyl acetate,
7: 3). We obtained 4.8 g (86%) of compound IV,
H20, 8.9), 3.18 d (1H, H20), 3.43 t (1H, H17, J17A,1
=
J17A,17B 10.5), 3.45 3.57 m (2H, C16H2), 3.75 d.d
17
_
(1H, H ), 4.45 d (1H, CH2Ph, 12.5), 4.54 d (1H,
11
_
CH2Ph), 5.31 s (1H, H ), 7.26 7.39 m (5H, C6H5).
13C NMR spectrum, C, ppm: 16.00 (C18), 17.37
(C6), 18.19 (C19), 19.51 (C9), 20.48 (C15), 21.16
(C14), 30.28 (C4), 33.16 (C13), 36.01 (C7), 36.30
(C10), 36.95 (C8), 37.96 (C4b), 38.17 (C3), 38.63
(C5), 39.91 (C10a), 45.59 (C2), 48.16 (C8a), 53.96
(C1), 54.91 (C4a), 61.07 (C17), 65.51 (C16), 73.12
20
11
[ ]2D0 77.9 (c 1.8, CHCl3). H NMR spectrum, ,
1
_
(C ), 79.65 (CH2Ph), 124.86 (C ), 127.39, 128.31,
138.99 (C6H5), 147.61 (C12).
ppm (J, Hz): 0.58 s (3H, C18H3), 0.74 s (3H, C19H3),
0.86 m (1H, H5), 1.03 d (3H, C14H3, 6.8), 1.07 d
(3H, C15H3, 6.8), 1.15 m (1H, H4), 1.27 1.42 m
(8H, H4a, H5, H6, C7H2, H8a, H9, H10), 1.54 m (2H,
H6, H9), 1.64 m (1H, H4), 1.91 m (1H, H10),
2.12 d.d.d (1H, H1, J1,2 8.3, J1,17A 12.3, J1,17B 4),
2.22 d.sept. (1H, H13, J13,11 1.3), 2.29 m (1H, H3),
2.46 d.d.d.d (1H, H2, J2,3 2.5), 2.90d (1H, H20, 8.9),
16 ,17 -5-Benzyloxymethyl-17-hydroxymethyl-
5, 9-dimethyl-13-isopropyl-14-oxapentacyclo
[11.4.1.01,10.04,9.012,17]octadecane (VI). To a solu-
tion of 0.26 g (0.47 mmol) of compound IV in 5 ml
of methanol at 0 C was added 0.5 ml of 5% solution
of HCl in methanol, and the mixture was stirred at
20 C for 1 h, evaporated, the residue was dissolved
in 5 ml of ethyl acetate, washed with saturated solu-
tion of NaHCO3 (2 5 ml), with water (5 ml), dried
on Na2SO4, evaporated, the residue was subjected to
chromatography (SiO2, eluent hexane ethyl acetate,
1: 1). We obtained 0.09 g (40%) of diol V and 0.11 g
3.19 d (1H, H20), 3.48 t (2H, H16, H17, J17A,1
=
J17A,17B = J16A,2 = J16A,16B 12.3), 3.98 d.d (1H,
H16, J16B,2 4), 4.25 d.d (1H, H17, J17B,1 4), 4.45 d
_
_
(1H, CH2Ph), 4.54 d (1H, CH2Ph, 12.5), 5.21 s
11
_
(CHPh), 5.41 s (1H, H ), 7.25 7.46 m (10H,
2C6H5). 13C NMR spectrum ( C, ppm): 16.15 (C18),
17.43 (C6), 18.26 (C19), 19.37 (C9), 20.52 (C15),
21.24 (C14), 29.70 (C4), 33.36 (C13), 36.08 (C7,
C10), 36.93 (C3), 37.01 (C8), 38.05 (C4b), 38.63
(C5), 39.82 (C10a), 45.24 (C2), 48.19 (C8a), 53.24
(C1), 55.13 (C4a), 71.89 (C17), 73.15 (C16), 74.74
1
(50%) of compound VI. H NMR spectrum, , ppm
(J, Hz): 0.74 s (3H, C18H3), 0.85 m (1H, H5), 0.91 s
(3H, C19H3), 0.92 d (3H, C14H3, 6.8), 0.97 d (3H,
C15H3, 6.8), 1.10 1.67 m (13H, H4, H4a, H5, C6H2,
C7H2, H8a, C9H2, H10, C11H2, H13), 1.76 m (2H,
H1, H4), 1.89 d.d (1H, H10, 11, 1.8), 2.07 m(1H,
H3), 2.36 d.t (1H, H2, J2,1 = J2,3 9.5, J2,16A 3.7,
J2,16B 0), 2.89 d (1H, H20, 8.9), 3.20 d (1H, H20),
3.48 d.d (1H, H16, J16A,16B 8.4), 3.67 t (1H, H17,
20
11
_
_
(C ), 79.59 (CH2Ph), 107.42 (CHPh), 124.91 (C ),
126.00, 127.47, 128.26, 128.34, 128.46, 139.09,
139.56 (2C6H5), 147.46 (C12).
5-Benzyloxymethyl-13 ,14 -dihydroxymethyl-
J17A,1 = J17A,17B 10.3), 3.84 d.d (1H, H17, J17B,1
5,9-dimethyl-16-isopropyltetracyclo[10.2.2.01,0.04,9]-
hexadec-15-ene (V). To a solution of 0.55 g
(1 mmol) of compound IV in 10 ml of methanol was
added 0.03 g (0.1 mmol) of pyridinium p-toluene-
16
_
3.8), 3.95 d (1H, H ), 4.45 d (1H, CH2Ph, 12.5),
_
4.54 d (1H, CH2Ph), 7.27 7.39 m (5H, C6H5).
13C NMR spectrum ( C, ppm): 15.79 (C18), 16.59
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 8 2001