Synthesis of Bistetrahydrofuran Derivatives
672 680
MS (FAB): m/z: 769 [M+H]+
;
HRMS (FAB): m/z: calcd for
m/z: 507 [M+Na]+
;
HRMS (FAB): m/z: calcd for C28H56NaO4Si:
C43H81O7SSi: 769.5472; found: 769.5484 [M+H]+.
507.3846; found: 507.3842 [M+Na]+.
(2R,5S,6R,9R,10R)-10-(tert-Butyldimethylsilyloxy)-2,5;6,9-diepoxy-1-do-
cosanol (13c): The procedure was the same as that used for preparation
of 13a and gave 13c as a colorless oil. [a]2D4 =+0.055 (c=0.91 in CHCl3);
1H NMR: d=0.05 (s,3H),0.07 (s,3H),0.86 0.88 (m,12H),1.26 1.50
(m,22H),1.59 1.76 (m,2H),1.82 2.04 (m,6H),2.69 (br,1H),3.46 (dd,
(2RS,4S)-4-[(3’R,4’S,7’S,8’R)-8’-(tert-Butyldimethylsilyloxy)-3’-(p-toluene-
sulfonyloxy)-4’,7’-epoxyicosanyl]-2-phenyl-1,3-dioxolane (15c): The pro-
cedure was the same as that used for preparation of 15a and gave 15c as
a colorless oil. [a]2D5 =À5.8 (c=1.19 in CHCl3); 1H NMR: d=À0.04 (s,
1.8H), À0.03 (s,1.2H), À0.003 (s,1.8H),0.002 (s,1.2H),0.84 0.85 (m,
9H),0.88 (t, J=6.7 Hz,3H),1.26 1.30 (m,22H),1.65 1.91 (m,8H),2.41
J=11.6,4.3 Hz,1H),3.57 (ddd,
J=6.7,5.2,4.3 Hz,1H),3.75 (dd,
J=
11.6,3.1 Hz,1H),3.91 (dt,
(dt, J=7.9,5.8 Hz,1H),4.06 4.10 ppm (m,1H);
J=6.7,5.8 Hz,1H),3.91 3.97 (m,1H),4.03
(s,1.8H),2.42 (s,1.2H),3.36 (ddd,
(m,1H),3.58 (dd, J=7.9,6.7 Hz,0.4H),3.65 (dd, J=7.3,6.7 Hz,0.6H),
J=11.6,5.5,3.1 Hz,1H),3.47 3.50
13C NMR (75 MHz):
d=À4.6, À4.3,14.1,18.2,22.7,25.6,25.9 (3C),27.3,27.4,29.0,29.4,29.59
(2C),29.63 (2C),29.7 (2C),29.9,31.9,32.8,65.7,74.8,79.8,81.1,82.2,
82.4 ppm; IR (KBr): n˜ =3442 cmÀ1; MS (FAB): m/z: 507 [M+Na]+
3.90 (ddd, J=11.6,7.3,4.9 Hz,1H),4.07 (dd,
4.18 (m,1H),4.23 (dd,
J=7.3,6.7 Hz,0.6H),4.12
J=7.3,4.3,
J=7.9,6.7 Hz,0.4H),4.66 (ddd,
;
3.7 Hz,0.6H),4.70 (ddd, J=7.3,4.3,3.7 Hz,0.4H),5.77 (s,0.6H),5.86 (s,
0.4H),7.25 7.30 (m,2H),7.37 7.41 (m,3H),7.45 7.48 (m,2H),7.77
7.81 ppm (m,2H); 13C NMR (75 MHz): d=À4.7, À4.3,14.1,18.1,21.5,
22.6,25.0,25.5,25.9 (3C),27.3,27.9 (0.6C),28.0 (0.4C),29.0 (0.4C),29.1
(0.6C),29.3,29.51,29.54,29.58 (2C),29.61,29.8,31.9,34.6,69.9 (0.6C),
70.5 (0.4C),72.8,76.2 (0.4C),76.9 (0.6C),79.2 (0.6C),79.3 (0.4C),82.5,
84.7 (0.6C),84.8 (0.4C),103.0 (0.4C),104.0 (0.6C),126.3,126.6,127.8
(2C),128.3 (2C),129.0 (0.4C),129.2 (0.6C),129.4 (2C),134.7 (0.4C),
HRMS (FAB): m/z: calcd for C28H56NaO4Si: 507.3846; found: 507.3828
[M+Na]+.
(2RS,4S)-4-[(3’S,4’R,7’R,8’R)-8’-(tert-Butyldimethylsilyloxy)-3’-(p-tolu-
enesulfonyloxy)-4’,7’-epoxyicosanyl]-2-phenyl-1,3-dioxolane (15b): The
procedure was the same as that used for preparation of 15a and gave
1
15b as a colorless oil. [a]2D1 =+8.2 (c=1.09 in CHCl3); H NMR: d=0.01
(s,3H),0.02 (s,3H),0.86 (s,9H),0.88 (t,
22H),1.57 1.94 (m,8H),2.41 (s,1.2H),2.43 (s,1.8H),3.43 (dt,
4.9 Hz,1H),3.55 (dd, J=7.9,6.1 Hz,0.4H),3.59 3.63 (m,1.6H),3.95
(dt, J=7.3,6.1 Hz,1H),4.05 (dd, J=7.9,6.7 Hz,0.4H),4.17 4.22 (m,
J=7.0 Hz,3H),1.25 1.43 (m,
134.8 (0.6C),137.7 (0.6),138.1 (0.4C),144.1 ppm; IR (KBr):
1460 cmÀ1; MS (FAB): m/z: 767 [M+Na]+ ; HRMS (FAB): m/z: calcd for
C42H68NaO7SSi: 767.4353; found: 767.4344 [M+Na]+.
n˜ =1599,
J=5.5,
1.6H),4.67 4.71 (m,1H),5.77 (s,0.4H),5.84 (s,0.6H),7.28 7.33 (m,
2H),7.35 7.39 (m,3H),7.44 7.47 (m,2H),7.78 7.81 ppm (m,2H);
13C NMR (75 MHz): d=À4.7, À4.3,14.1,18.1,21.5,22.6,25.4,25.9 (3C),
27.3,27.7,27.88 (0.4C),27.95 (0.6C),28.2 (0.6C),28.4 (0.4C),29.3,29.56
(2C),29.58 (2C),29.6,29.8,31.9,32.97 (0.4C),33.01 (0.6C),69.8 (0.4C),
70.4 (0.6C),74.9,75.7 (0.6C),76.3 (0.4C),79.3 (0.6C),79.4 (0.4C),82.1,
84.0 (0.4C),84.1 (0.6C),103.0 (0.6C),104.0 (0.4C),126.3,126.6,127.72,
127.74,128.2,128.3,129.0 (0.6C),129.2 (0.4C),129.5 (2C),134.7,137.7
(2S,5S,6S,9S,10R)-10-(tert-Butyldimethylsilyloxy)-2,5;6,9-diepoxy-1-doco-
sanol (13 f): The procedure was the same as that used for preparation of
13b and gave 13 f as a colorless oil. [a]2D3 =À0.59 (c=1.18 in CHCl3);
1H NMR: d=0.035 (s,3H),0.044 (s,3H),0.85 0.87 (m,12H),1.23 1.34
(m,22H),1.55 1.73 (m,3H),1.78 1.97 (m,5H),2.21 (br,1H),3.47 (dd,
J=11.6,5.5 Hz,1H),3.67 (dt,
3.81 3.89 (m,2H),3.89 3.93 (m,1H),4.06 4.10 ppm (m,1H);
J=11.6,2.4 Hz,1H),3.79 3.80 (m,1H),
13C NMR
(75 MHz): d=À4.6, À4.3,14.1,18.1,22.6,25.4 (2C),25.9 (3C),27.4,28.6
(0.4C),138.2 (0.6C),144.3 ppm; IR (KBr):
n˜ =1599,1460 cm À1; MS
(2C),29.3,29.5,29.55,29.59 (2C),29.62,29.8,31.9,34.8,64.6,73.4,79.7,
(FAB): m/z: 767 [M+Na]+ ; HRMS (FAB): m/z: calcd for C42H68NaO7S-
Si: 767.4353; found: 767.4373 [M+Na]+.
81.8,82.0,82.3 ppm; IR (KBr):
n˜ =3344 cmÀ1; MS (FAB): m/z: 507
[M+Na]+ ; HRMS (FAB): m/z: calcd for C28H56NaO4Si: 507.3846; found:
507.3852 [M+Na]+.
(2S,5R,6R,9R,10R)-10-(tert-Butyldimethylsilyloxy)-2,5;6,9-diepoxy-1-do-
cosanol (13d): The procedure was the same as that used for preparation
of 13b and gave 15d as a colorless oil. [a]2D0 =+14.6 (c=0.82 in CHCl3);
(2S,5S,6S,9S,10R)-10-(tert-Butyldimethylsilyloxy)-2,5-dihydroxy-6,9-epoxy-
docosanyl 2,4,6-triisopropylbenzenesulfonate (11d): The procedure was
the same as that used for preparation of 11a and gave 11d as a colorless
oil. [a]2D6 =À6.5 (c=1.13 in CHCl3); 1H NMR: d=0.03 (s,3H),0.04 (s,
3H),0.86 0.88 (m,12H),1.25 1.63 (m,44H),1.76 1.98 (m,4H),2.77
(br,1H),2.91 (sep, J=6.7 Hz,1H),3.37 (ddd, J=9.2,6.7,2.1 Hz,1H),
1H NMR: d=0.05 (s,3H),0.07 (s,3H),0.87 (t,
J=6.1 Hz,3H),0.88 (s,
9H),1.26 1.52 (m,22H),1.69 1.81 (m,2H),1.84 1.96 (m,6H),2.73
2.77 (m,1H),3.45 3.47 (m,1H),3.62 (ddd, J=7.6,4.9,4.3 Hz,1H),3.77
(dd, J=11.6,2.7 Hz,1H),3.89 3.93 (m,2H),4.01 (dt, J=7.6,5.8 Hz,
1H),4.10 4.13 ppm (m,1H); 13C NMR (75 MHz): d=À4.6, À4.3,14.1,
18.1,22.7,25.6,25.9 (3C),27.1,27.3,28.7,28.9,29.3,29.59 (2C),29.61
(2C),29.7,29.9,31.9,32.6,65.7,74.5,80.0,81.5,81.6,82.3 ppm; IR
3.47 (br,1H),3.73 3.77 (m,2H),3.84 (ddd,
3.88 3.93 (m,1H),3.97 (dd, J=9.8,6.4 Hz,1H),4.00 (dd, J=9.8,4.9 Hz,
1H),4.14 (sep, J=6.7 Hz,2H),7.18 ppm (s,2H);
13C NMR (67.8 MHz):
J=7.9,6.1,3.7 Hz,1H),
(KBr): n˜ =3446 cmÀ1; MS (FAB): m/z: 507 [M+Na]+ ; HRMS (FAB): m/
z: calcd for C28H57O4Si: 485.4026; found: 485.4032 [M+Na]+.
d=À4.4, À4.1,14.2,18.2,22.7,23.6 (2C),24.78 (2C),24.80 (2C),25.5,
26.0 (3C),26.2,28.5,29.4,29.5,29.61,29.63,29.68 (4C),29.72,29.9,30.0,
32.0,34.3,34.8,69.4,72.7,73.1,74.1,82.0,82.3,123.7 (2C),129.0,150.7
(2C),153.6 ppm; IR (KBr): n˜ =3417 cmÀ1; MS (FAB): m/z: 769 [M+H]+
; HRMS (FAB): m/z: calcd for C43H81O7SSi: 769.5472; found: 769.5488
[M+H]+.
(2S,5R,6S,9S,10R)-10-(tert-Butyldimethylsilyloxy)-2,5-dihydroxy-6,9-ep-
oxydocosanyl 2,4,6-triisopropylbenzenesulfonate (11c): The procedure
was the same as that used for preparation of 11a and gave 11c as a color-
less oil. [a]2D2 =À4.9 (c=1.71 in CHCl3); 1H NMR: d=0.03 (s,3H),0.05
(s,3H),0.86 0.89 (m,12H),1.25 1.63 (m,43H),1.70 1.93 (m,5H),2.29
(2R,5S,6S,9S,10R)-10-(tert-Butyldimethylsilyloxy)-2,5;6,9-diepoxy-1-doco-
sanol (13g): The procedure was the same as that used for preparation of
13a and gave 13g as a colorless oil. [a]2D5 =À10.4 (c=1.03 in CHCl3);
1H NMR: d=0.038 (s,3H),0.044 (s,3H),0.85 0.87 (m,12H),1.24 1.34
(br,1H),2.83 (br,1H),2.91 (sep,
J=6.7 Hz,1H),3.72 3.76 (m,2H),
3.82 (ddd, J=9.2,5.5,3.7 Hz,1H),3.89 (ddd,
3.93 3.97 (m,2H),4.02 4.05 (m,1H),4.13 (sep,
J=9.2,5.5,3.7 Hz,1H),
J=6.7 Hz,2H),
7.19 ppm (s,2H); 13C NMR (75 MHz): d=À4.5, À4.3,14.1,18.1,22.6,
23.5 (2C),24.66 (2C),24.68 (2C),25.4,25.5,25.9 (3C),27.9,29.3,29.50,
29.53 (2C),29.57 (3C),29.61 (2C),29.7,29.8,31.9,34.2,34.5,69.1,72.0,
72.5,73.4,82.2,82.5,123.8 (2C),129.0,150.8 (2C),153.8 ppm; IR (KBr):
n˜ =3431 cmÀ1; MS (FAB): m/z: 769 [M+H]+ ; HRMS (FAB): m/z: calcd
for C43H81O7SSi: 769.5472; found: 769.5511 [M+H]+.
(m,22H),1.75 2.03 (m,8H),3.09 (br,1H),3.44 (dd,
J=11.6,3.1 Hz,
1H),3.76 (dd, J=11.6,2.4 Hz,1H),3.80 3.83 (m,1H),3.88 3.94 (m,
3H),4.10 4.14 ppm (m,1H); 13C NMR (75 MHz): d=À4.6, À4.3,14.1,
18.1,22.7,25.3,25.6,25.9 (3C),27.6,28.9,29.2,29.3,29.53,29.55,29.60
(2C),29.64,29.8,31.9,34.7,66.1,73.0,79.9,81.4,81.5,82.8 ppm; IR
(KBr): n˜ =3421 cmÀ1; MS (FAB): m/z: 485 [M+H]+ ; HRMS (FAB): m/z:
calcd for C28H57O4Si: 485.4026; found: 485.4027 [M+H]+.
(2R,5R,6S,9S,10R)-10-(tert-Butyldimethylsilyloxy)-2,5;6,9-diepoxy-1-do-
cosanol (13e): The procedure was the same as that used for preparation
of 13a and gave 13e as a colorless oil. [a]2D3 =À10.5 (c=1.12 in CHCl3);
1H NMR: d=0.05 (s,6H),0.86 0.88 (m,12H),1.25 1.36 (m,22H),1.65
(2RS,4S)-4-[(3’S,4’S,7’S,8’R)-8’-(tert-Butyldimethylsilyloxy)-3’-(p-toluene-
sulfonyloxy)-4’,7’-epoxyicosanyl]-2-phenyl-1,3-dioxolane (15d): The pro-
cedure was the same as that used for preparation of 15a and gave 15d as
a colorless oil. [a]2D3 =À1.1 (c=1.39 in CHCl3); 1H NMR: d=À0.07 (s,
1.8H), À0.06 (s,1.2H), À0.011 (s,1.8H), À0.007 (s,1.2H),0.84 0.85 (m,
9H),0.88 (t, J=7.0 Hz,3H),1.26 1.30 (m,22H),1.61 1.94 (m,8H),
2.07 (m,9H),3.48 (ddd, J=11.6,6.1,5.5 Hz,1H),3.65 (ddd,
J=11.6,6.7,
3.1 Hz,1H),3.75 3.78 (m,1H),3.87 (dt, J=8.5,6.1 Hz,1H),3.90 (ddd,
J=8.5,6.7,3.7 Hz,1H),3.94 (dt,
J=6.7,6.1 Hz,1H),4.08 4.13 ppm (m,
1H); 13C NMR (75 MHz): d=À4.5, À4.3,14.1,18.1,22.7,25.4,25.6,25.9
2.415 (s,1.8H),2.423 (s,1.2H),3.55 3.58 (m,1.4H),3.64 (dd,
6.7 Hz,0.6H),3.67 3.71 (m,1H),3.95 4.00 (m,1H),4.06 (dd,
J=7.9,
J=7.9,
(3C),27.3,28.7,28.8,29.3,29.5,29.56,29.61 (2C),29.64,29.8,31.9,34.7,
64.9,73.4,79.9,81.4,81.5,82.4 ppm; IR (KBr):
n˜ =3460 cmÀ1; MS (FAB):
6.7 Hz,0.6H),4.17 4.23 (m,1H),4.22 (dd,
J=6.7,6.1 Hz,0.4H),4.58
679
Chem. Eur. J. 2004, 10,672 680
¹ 2004 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim