Natural erythro-(1R,2S)-8-O-40-neolignan myrislignan
95
extracted with EtOAc. The organic layer was washed with
saturated NaHCO3 and NaCl solution, dried over MgSO4,
and concentrated in vacuo. Flash chromatography of the
residue over silica gel afforded 7.6 g (83%) 6 as amor-
quenched with water, filtered, and concentrated in vacuo.
Flash column chromatography of the residue over silica gel
gave 3.1 g (82%) 8 as a colorless liquid in 93% ee.
[a]2D0 = ?31.8° cm3 g-1 dm-1 (c = 0.3, CHCl3); IR
(KBr): m = 3,418, 2,936, 2,869, 1,593, 1,513, 1,457,
1,418, 1,380, 1,263, 1,226, 1,137, 1,075, 1,028,
809 cm-1 1H NMR (300 MHz, CDCl3): d = 1.00 (d,
;
phous powder with 95% ee. Mp: 130–132 °C; [a]D20
=
ꢀ
?42.3° cm3 g-1 dm-1 (c = 0.5, CHCl3); IR (KBr): m =
3,420, 2,941, 2,845, 1,641, 1,520, 1,422, 1,318, 1,235,
1,102, 1,023 cm-1; 1H NMR (300 MHz, CDCl3): d = 2.44
(s, 3H, ArCH3), 3.90 (s, 3H, ArOCH3), 3.84–3.96 (m, 1H,
CHOHCH2OTs), 3.98–4.11 (m, 2H, CH2OTs), 4.60 (d, 1H,
J = 6.0 Hz, ArCHOH), 5.14 (s, 2H, ArCH2OAr),
6.72–7.76 (m, 12H, Ar) ppm; 13C NMR (75 MHz, CDCl3):
d = 21.6 (ArCH3), 56.0 (OCH3), 70.3 (CH2OTs), 70.9
(CHOHCH2OTs), 73.4 (ArCH2OAr), 73.7 (ArCHOHCH),
109.9, 113.7, 118.8, 127.2, 127.2, 127.9, 127.9, 128.6,
128.6, 129.9, 129.9, 132.5, 132.5, 136.9, 136.9, 146.1,
148.1, 149.8 ppm; EI-MS: m/z = 458 (M?, 2.4), 286 (1.2),
268 (0.7), 243 (4.8), 123 (7.8), 91 (100); HRMS: calcd for
C24H30NO7S (M ? NH4?) 476.1738, found 476.1732.
ꢀ
3H, J = 7.0 Hz, OHCHCH3), 1.44–1.72 (m, 6H, CH2),
3.20 (m, 1H, CH2CH2O), 3.45 (m, 1H, CH2CH2O), 3.89 (s,
3H, OCH3), 3.84–4.05 (m, 1H, CHOHCH3), 4.16 (d, 1H,
J = 7.5 Hz, ArCHOTHP), 4.84 (s, 1H, OCHO), 5.14 (s,
2H, ArCH2OAr), 6.82–6.90 (m, 3H, Ar), 7.30–7.44 (m, 5H,
Ar) ppm; 13C NMR (75 MHz, CDCl3): d = 18.2
(CH2CH2), 19.3 (HOCHCH3), 25.2 (CH2CH2), 30.5
(CH2CH2), 55.9 (CH3O), 62.4 (CH2OCH), 71.0
(CH3CHOH), 71.1 (ArCH2O), 85.7 (ArCHOTHP), 100.0
(OCHO), 110.8, 113.4, 119.7, 127.3, 127.3, 127.8, 128.5,
128.5, 133.3, 137.1, 147.6, 149.3 ppm; EI-MS: m/z = 372
(M?, 0.4), 328 (1.6), 288 (0.3), 271 (0.6), 243 (37), 91 (98),
?
85 (100); HRMS: calcd for C22H32NO5 (M ? NH4
)
threo-(1R,2R)-1-(4-Benzyloxy-3-methoxyphenyl)-2,3-
epoxy-1-propanol (7, C17H18O4)
390.2273, found 390.2275.
Compound 6 (6.9 g, 15 mmol) was added to a solution of
2.1 g K2CO3 (15 mmol) in methanol. The mixture was
stirred at room temperature for 5 h and concentrated in
vacuo. The residue was dissolved in EtOAc, then washed
with water and saturated NaCl aqueous solution for three
times. The extract was dried over MgSO4 and concentrated
in vacuo. Flash column chromatography of the residue over
silica gel afforded 4.1 g (95%) 7 as a colorless liquid in
92% ee. [a]2D0 = ?36.2° cm3 g-1 dm-1 (c = 0.6, CHCl3);
threo-(1R,2R)-1-[3-Methoxy-4-(methoxymethoxy)phenyl]-
1-(tetrahydropyran-2-yloxy)-2-propanol (13, C17H26O6)
Palladized charcoal (10%, 80 mg) was added to a stirred
solution of 2.2 g 8 (6 mmol) in 20 cm3 methanol. After
stirring for 4 h at room temperature under atmospheric
pressure of hydrogen, the solvent was filtered and
concentrated under reduced pressure. A solution of 0.6 g
MOMCl (6 mmol) was added (in one go) to a rapidly
stirred mixture of the resulting residue and 1.2 g K2CO3
(8 mmol) in 40 cm3 acetone under N2 at room temper-
ature. The mixture was stirred for 3 h and quenched with
water. The aqueous layer was extracted with ethyl acetate
and the extracts were washed with brine and dried with
Na2SO4. Then the solvent was removed in vacuo and
flash column chromatography of the residue over silica
gel afforded 1.8 g (90%) 13 as a colorless liquid.
[a]2D0 = ?28.7° cm3 g-1 dm-1 (c = 0.2, CHCl3); IR
ꢀ
IR (KBr): m = 3,450, 2,983, 2,936, 2,840, 1,732, 1,604,
1
1,592, 1,512, 1,465, 1,262, 1,140, 1,027, 916 cm-1; H
NMR (300 MHz, CDCl3): d = 2.80–2.89 (m, 2H,
CHOCH2), 3.16–3.25 (m, 1H, CHCH2O), 3.97 (s, 3H,
OCH3), 4.43 (d, 1H, J = 5.8 Hz, ArCHOHCH), 5.17 (s,
2H, ArCH2OAr), 6.87–7.45 (m, 8H, ArH) ppm; 13C NMR
(75 MHz, CDCl3): d = 45.6 (CHCH2O), 56.2 (OMe-3),
56.7 (CHCH2O), 71.3 (ArCH2OAr), 74.8 (ArCHOHCH),
109.3, 113.9, 121.5, 126.7, 127.2, 127.2, 127.9, 128.5,
128.5, 137.1, 147.3, 149.6 ppm; EI-MS: m/z = 286 (M?,
5), 243 (0.7), 165 (0.4), 123 (0.2), 91 (100); HRMS: calcd
for C17H22NO4 (M ? NH4?) 304.1544, found 304.1547.
ꢀ
(KBr): m = 3,452, 2,943, 2,852, 1,602, 1,513, 1,467,
1,382, 1,263, 1,135, 1,028, 902 cm-1 1H NMR
;
(500 MHz, CDCl3): d = 1.06 (d, 3H, J = 7.0 Hz,
OHCHCH3), 1.47–1.78 (m, 6H, CH2), 3.20 (m, 1H,
CH2CH2O), 3.43 (m, 1H, CH2CH2O), 3.52 (s, 3H,
OCH3), 3.85–4.02 (m, 4H, CHOHCH3, OCH3), 4.15 (d,
1H, J = 8.0 Hz, ArCHOTHP), 4.87 (s, 1H, OCHO), 5.29
(s, 2H, CH3OCH2OAr), 6.85–7.10 (m, 3H, Ar) ppm; 13C
NMR (75 MHz, CDCl3): d = 17.8 (CH2CH2), 19.5
(HOCHCH3), 24.9 (CH2CH2), 31.2 (CH2CH2), 55.7
(CH3O), 56.9 (CH3OCH2Ar), 62.4 (CH2OCH), 71.8
(CH3CHOH), 82.7 (ArCHOTHP), 95.8 (CH3OCH2Ar),
100.2 (OCHO), 111.8, 116.5, 120.2, 123.8, 144.3,
149.7 ppm; EI-MS: m/z = 326 (M?, 3.8), 294 (12.3),
threo-(1R,2R)-1-(4-Benzyloxy-3-methoxyphenyl)-1-(tetra-
hydropyran-2-yloxy)-2-propanol (8, C22H28O5)
Dihydropyran (0.9 g, 10 mmol) and a catalytic amount of
pyridinium p-toluenesulfonate were added to a solution of
2.9 g 7 (10 mmol) in dry CH2Cl2 and the mixture was
stirred at room temperature until TLC revealed the absence
of 7. Then the solvent was evaporated under reduced
pressure and the residue was added to a solution of 0.6 g
LiAlH4 (15 mmol) in an appropriate amount of dry THF.
The mixture was stirred at room temperature for 24 h,
123