2756 J. Am. Chem. Soc., Vol. 122, No. 12, 2000
Jaeger et al.
of 1b and 2b during workup did not affect the 15b/16b ratio and the
yield of 15b + 16b.
(m, 10H, CH
(CH , (CH
3H, (CH Si(CH
2
CH N), 1.27 (m, 30H, 2 (CH
), 0.89 (t, 6H, 2 CH Si), 0.16 (s,
3 a 3 b
), 0.15 (s, 3H, (CH ) Si(CH ) ); C NMR δ 175.06,
2
S, 2 CH
2
CH
2
O, 2 CH
2
CH
2
2 2
) ,
)
2 5
2
)
6
3
), 0.73 (m, 2H, CH
2
13
(
c) 1b and 2b with Sodium Salicylate. The procedure for run 13 is
as follows, and those for other runs were analogous. A mixture of 10.9
mg (0.0207 mmol) of 1b and 0.70 mL of H O was sonicated at 25 °C
for ca. 15 min to give a cloudy solution, followed by the addition of
5.6 mg (0.0790 mmol) of 2b and 0.78 mg (0.0047 mmol) of 4-tert-
)
3 a
)
3 b
174.56, 139.35, 138.30, 65.06, 65.04, 59.98, 59.96, 45.69, 42.42, 41.94,
34.47, 34.19, 33.92, 32.17, 32.14, 32.01, 30.00, 29.92, 29.59, 29.55,
29.43, 29.27, 28.81, 28.78, 27.82, 27.33, 26.09, 26.06, 24.27, 22.91,
22.86, 16.49, 14.35, 14.31, -1.35, -1.43. FAB HRMS (3-nitrobenzyl
2
3
butylcatechol. After the resultant cloudy mixture was stirred at 25 °C
for ca. 5 min, it became clear. Then 13.5 mg (0.0843 mmol) of sodium
salicylate (Aldrich) was added to give a clear solution with greater
viscosity that was stirred at 25 °C for 46 h. The reaction mixture was
alcohol matrix) calcd for C42
739.5834. For 19b: 1H NMR δ 4.02-4.14 (m, 4H, 2 CH
2.92 (m, 1H), 2.20-2.79 (m containing s at 2.25, 23H total including
2 (CH NCH CH S, 2 CH CH O, 2 CH
CH N), 1.28 (m, 30H, 2 (CH , (CH ), 0.89 (t, 6H, 2 CH
0.74 (m, 2H, CH Si), 0.16 (s, 3H, (CH Si(CH ), 0.15 (s, 3H, (CH
H N O
83 2 4
SSi (M + H) 739.5843, found
2
O), 2.83-
3
)
2
2
), 1.41-1.68 (m, 10H, CH
, (CH
2
2
2
2
2
-
diluted with MeCN and rotary evaporated at ca. 45 °C to leave an
2
2
)
2
2
)
5
2
)
6
3
),
1
amorphous solid, which was analyzed by H NMR (400 MHz, CDCl
3
)
2
)
3 a
)
3 b
3 a
) -
13
and analytical HPLC (eluant ) 0.020 M ammonium trifluroacetate in
MeCN-H O (80/20 to 95/5 during 20 min); flow rate ) 1.0 mL/min;
3 b
Si(CH ) ); C NMR δ 175.07, 174.54, 139.38, 138.23, 65.14, 64.95,
59.97, 45.68, 42.42, 41.92, 34.43, 34.19, 33.92, 32.17, 32.12, 32.01,
30.02, 29.92, 29.58, 29.55, 29.43, 29.27, 28.80, 27.83, 27.33, 26.08,
24.27, 22.90, 22.86, 16.49, 14.35, 14.31, -1.34, -1.43. FAB HRMS
2
retention times ) 6.6 min for 2b, 18.8 min for 16b, 19.8 min for 1b,
and 22.8 min for 15b). The results are given in runs 11-14 of Table
1
.
(3-nitrobenzyl alcohol matrix) calcd for C42
39.5843, found 739.5837.
trans-1-[(2-Trimethylammonio)ethylthio]-2-(dimethyldodecyl-
83 2 4
H N O SSi (M + H)
7
(d) 7a and 14a. The results for 7a and 14a are given in runs 15 and
1
1
6 of Table 1. The following procedure is for run 16, and that for run
5 was analogous. A solution of 54.0 mg (0.141 mmol) of 7a, 114 mg
silyl)-4-(dodecoxycarbonyl)-5-[(2-trimethylammonio)ethoxycarbonyl]-1-cyclo-
hexene Diiodide (15a). A mixture of 38.3 mg (0.0518 mmol) of 18a,
72.5 mg (0.511 mmol) of MeI, and 2.0 mL of MeCN was stirred at 25
(
0.321 mmol) of 14a, and 2.27 mg (0.0137 mmol) of 4-tert-
butylcatechol in 2.15 mL of C Me was stirred at 80 °C for 48 h.
6
H
5
The reaction mixture was rotary evaporated to leave a heavy oil, which
°C under N
(99%) of 15a as an amorphous solid: H NMR δ 4.69 (m, 2H, OCH
CH N), 4.28 (m, 2H, OCH CH N), 4.06 (m, 2H, CH CH CH
(m, 2H, SCH CH N), 3.57 (s, 18H, 2 (CH N), 3.24 (m, 2H, SCH
CH
(m, 1H), 1.61 (m, 2H, CH
0.89 (t, 6H, 2 CH ), 0.71 (m, 2H, CH
0.18 (s, 3H, (CH
2
overnight and then rotary evaporated to leave 52.3 mg
1
was chromatographed (MPLC) on silica gel with hexanes-EtOAc-
2
-
Et
3
N (100:0:0 to 70:28:2) as eluant to give 49.2 mg (47%) of trans-
2
2
2
2
2
2
O), 3.70
1-[2-(N,N-dimethylamino)ethylthio]-2-(dimethyldodecylsilyl)-4-[2-(N,N-
2
2
)
3 3
2
-
dimethylamino)ethoxycarbonyl]-5-(dodecoxycarbonyl)-1-cyclohex-
ene (19a) as a yellow oil, followed by 38.4 mg (37%) of trans-1-[2-
2
N), 3.06 (m, 1H), 2.89 (m, 2H), 2.71 (m, 1H), 2.60 (m, 1H), 2.23
CH CH O), 1.26 (m, 38H, (CH , (CH
Si), 0.19 (s, 3H, (CH Si(CH
); C NMR δ 174.78, 173.52, 141.38,
2
2
2
)
2 9
2
)10),
(
(
N,N-dimethylamino)ethylthio]-2-(dimethyldodecylsilyl)-4-
3
2
)
3 a
3 b
) ),
13
dodecoxycarbonyl)-5-[2-(N,N-dimethylamino)ethoxycarbonyl]-1-
3 a 3 b
) Si(CH )
1
136.34, 66.43, 65.25, 65.12, 58.47, 54.96, 54.25, 41.72, 41.37, 34.78,
34.07, 33.91, 32.04, 29.90, 29.81, 29.77, 29.61, 29.49, 29.43, 28.72,
26.03, 25.04, 24.14, 22.81, 16.45, 14.26, -1.31, -1.43. FAB HRMS
(3-nitrobenzyl alcohol matrix) calcd for C44
cyclohexene (18a) as an amorphous solid. For 18a: H NMR δ 4.28
(
2
2
t, J ) 5.6, 2H, CH
2
CH
.98 (m containing s at 2.41, 24H, SCH
CH , 2 CH), 1.61 (m, 2H, CH CH
10), 0.88 (t, 6H, 2 CH ), 0.73 (m, 2H, CH
Si(CH ), 0.16 (s, 3H, (CH
2
CH
2
O), 4.08 (m, 2H, OCH
CH N, OCH CH
CH O), 1.25 (m, 38H, (CH
Si), 0.17 (s, 3H, (CH
2
CH
2
N), 2.18-
2
2
2
2
N, 2 (CH
3
)
2
N,
-
2
)
9
,
H
88
N
2
O
4
SSiI (monocation‚I )
2
2
2
2
(CH
2
)
3
2
3 a
) -
895.5280, found 895.5257.
1
3
)
b
3
)
a
Si(CH
3
)
b
); C NMR δ 174.81, 174.26,
trans-1-[(2-Trimethylammonio)ethylthio]-2-(dimethyldodecyl-
silyl)-4-[(2-trimethylammonio)ethoxycarbonyl]-5-(dodecoxycarbonyl)-1-cyclo-
hexene Diiodide (16a). From 19a, the same procedure as for 15a gave
3
1
3
2
39.62, 138.05, 65.19, 62.03, 58.93, 57.47, 45.46, 44.94, 42.09, 41.67,
3.96, 33.93, 32.14, 29.97, 29.89, 29.85, 29.82, 29.79, 29.66, 29.58,
9.49, 28.81, 26.09, 24.26, 22.91, 16.49, 14.35, -1.34, -1.42. FAB
(98%) 16a as an amorphous solid: 1H NMR δ 4.81 (m, 1H, OCH
H -
a b
HRMS (3-nitrobenzyl alcohol matrix) calcd for C42
H) 739.5843, found 739.5838. For 19a: H NMR δ 4.26 (t, J ) 5.7,
H
83
N
2
O
4
SSi (M +
CH
2
N), 4.41 (m, 1H, OCH
a b
H
CH
2
N), 3.98-4.14 (m, 4H, OCH
CH N), 3.51-3.63 (2 s at 3.55
N, SCH CH N), 3.10-
3.36 (m, 3H), 3.00 (m, 1H), 2.70 (m, 2H), 2.51 (m, 1H), 2.39 (m, 1H),
1.63 (m, 2H, CH CH CH O), 1.26 (m, 38H, (CH , (CH 10), 0.88 (t,
6H, 2 CH ), 0.69 (m, 2H, CH Si), 0.19 (s, 6H, (CH
2 2
CH N,
1
CH
2
CH CH O), 3.81 (m, 1H, SCH
2
2
2
a b
H
2
2
2
1
6
H, CH
.76-2.84 (m, 3H), 2.63-2.74 (m, 3H), 2.48-2.62 (m, 3H), 2.18-
.47 (m containing 2 s at 2.35 and 2.36, 14H total including 2 (CH N),
.60 (m, 2H, CH CH CH O), 1.25 (m, 38H, (CH , (CH 10), 0.88 (t,
H, 2 CH ), 0.73 (m, 2H, CH Si), 0.16 (s, 3H, (CH Si(CH ), 0.15
); C NMR δ 174.94, 174.25, 139.55, 138.26,
5.28, 62.31, 59.09, 57.64, 45.61, 45.11, 42.18, 41.57, 33.95, 33.87,
2
CH
2
CH
2
O), 4.08 (m, 2H, OCH
2
2
CH N), 2.88-2.97 (m, 1H),
and 3.59, overlapping with m, 19H, 2 (CH
3
)
3
2
a b
H
)
3 2
2
2
2
2
)
9
2
)
1
3
2
)
9
2
)
3
2
3 2
) Si); C NMR δ
2
2
2
)
a
)
3 b
174.37, 173.80, 143.32, 134.85, 66.44, 65.81, 65.46, 58.09, 55.31, 54.09,
41.59, 40.80, 33.98, 33.58, 33.38, 32.15, 29.98, 29.95, 29.91, 29.82,
29.67, 29.59, 28.80, 26.16, 24.16, 24.03, 22.92, 16.71, 14.37, -1.10,
-1.17. FAB HRMS (3-nitrobenzyl alcohol matrix) calcd for C44
SSiI (monocation‚I ) 895.5280, found 895.5286.
trans-1-[(6-Trimethylammonio)hexylthio]-2-(dimethyloctylsilyl)-
4-(octoxycarbonyl)-5-[(6-trimethylammonio)hexoxycarbonyl]-1-cy-
clohexene Diiodide (15b). A mixture of 15.0 mg (0.0203 mmol) of
18b, 17.7 mg (0.125 mmol) of MeI, and 0.80 mL of MeCN was stirred
3
2
3
1
3
3 a 3 b
(s, 3H, (CH ) Si(CH )
6
3
2
2.12, 29.95, 29.87, 29.84, 29.76, 29.64, 29.56, 29.48, 28.93, 28.79,
6.08, 24.25, 22.90, 16.49, 14.33, -1.34, -1.44. FAB HRMS (3-
H
88
N
2
O
4
-
-
nitrobenzyl alcohol matrix) calcd for C42
83 2 4
H N O SSi (M + H) 739.5843,
found 739.5839.
(e) 7b and 14b. The results for 7b and 14b are given in runs 17 and
1
1
8 of Table 1. The following procedure is for run 18, and that for run
7 was analogous. A solution of 66.5 mg (0.173 mmol) of 7b, 152 mg
at 25 °C under N
purified by TLC (0.25-mm aluminum oxide; EM 5731-3) with 60:38:2
MeCN-CH Cl -MeOH as eluant to give 12.3 mg (59%) of 15b as
an amorphous solid: H NMR δ 4.00-4.24 (m, 4H, 2 CH
3.80 (m, 4H, 2 CH N), 3.46 (s, 18H, 2 (CH N), 2.87-2.94 (m, 1H),
2.18-2.79 (m, 7H), 1.76-1.89 (m, 4H, 2 CH CH N), 1.20-1.72 (m,
36H, 2 (CH , (CH ), 0.89 (t, 6H, 2 CH ), 0.72 (m, 2H, CH Si),
0.17 (s, 3H, (CH Si(CH ), 0.16 (s, 3H, (CH ); C NMR
2
overnight. The residue after rotary evaporation was
(
0.428 mmol) of 14b, and 3.14 mg (0.0189 mmol) of 4-tert-
butylcatechol in 1.5 mL of C Me was stirred at 85 °C for 24 h. The
6
H
5
2
2
1
reaction mixture was rotary evaporated to leave a heavy oil, which
was analyzed by analytical HPLC (eluant ) 0.020 M ammonium
trifluroacetate in MeCN; flow rate ) 1.0 mL/min; retention times )
2
O), 3.69-
2
3 3
)
2
2
6
(
2
.0 min for 19b and 7.7 min for 18b) and then chromatographed
MPLC) on silica gel with hexanes-EtOAc-Et N (100:0:0 to 60:20:
0) as eluant to give 46 mg (36%) of trans-1-[6-(N,N-dimethylamino)-
)
2 3
)
2 6
3
2
1
3
3
)
a
3
)
b
3 a 3 b
) Si(CH )
3
δ 175.09, 174.52, 139.23, 138.40, 66.90, 65.09, 64.61, 54.00, 42.22,
41.74, 34.28, 33.94, 33.88, 32.14, 31.97, 31.88, 29.93, 29.54, 29.50,
29.39, 28.76, 28.70, 28.40, 26.05, 25.69, 25.42, 24.21, 23.26, 23.13,
22.87, 22.83, 14.35, 14.30, -1.39, -1.45. FAB HRMS (3-nitrobenzyl
hexylthio]-2-(dimethyloctylsilyl)-4-[6-(N,N-dimethylamino)hexoxycar-
bonyl]-5-(octoxycarbonyl)-1-cyclohexene (19b) as a heavy oil, followed
by 43 mg (34%) of trans-1-[6-(N,N-dimethylamino)hexylthio]-2-
(
dimethyloctylsilyl)-4-(octoxycarbonyl)-5-[2-(N,N-dimethylamino)hex-
alcohol-glycerol-trifluoroacetic acid matrix) calcd for C44
88 2 4
H N O SSiI
1
-
oxycarbonyl]-1-cyclohexene (18b) as a heavy oil. For 18b: H NMR
δ 4.02-4.14 (m, 4H, 2 CH O), 2.83-2.92 (m, 1H), 2.21-2.79 (m
containing s at 2.25, 23H total including 2 (CH NCH ), 1.41-1.69
(monocation‚I ) 895.5280, found 895.5255.
2
trans-1-[(6-Trimethylammonio)hexylthio]-2-(dimethyloctylsilyl)-
4-[(6-trimethylammonio)hexoxycarbonyl]-5-(octoxycarbonyl)-1-cy-
)
3 2
2