Lepore et al.
[2-Methyl-(1,4,7,10,13-pentaoxocyclopentadecyl)] 2-
10H), 3.54-3.52 (m, 2H), 3.36 (s, 3H), 2.70 (t, 2H, J ) 7.3 Hz),
2.04-1.97 (m, 2H); 13C NMR (100.75 MHz, CDCl3) δ 167.0,
140.6, 134.2, 133.8, 133.8, 133.7, 133.5, 131.0, 130.1, 130.0,
129.8, 129.8, 128.7, 128.6, 128.6, 126.4, 72.1, 71.2, 71.0, 70.8,
70.7, 70.6, 70.6, 68.9, 68.8, 65.6, 59.3; HRMS (EI) [M + Na]+:
calcd for C25H34O9SNa 533.1816, found 533.1836.
3-Phenylpropyl [2-Methyl-(1,4,7,10-tetraoxocyclodode-
cylcarboxy)]-1-benzosulfonate (3a): (0.51 g, 82%); IR (neat)
1728 (CdO), 1373, 1198 (SO2) cm-1; 1HNMR (400 MHz, CDCl3)
δ 7.99 (d, 1H, J ) 7.73 Hz), 7.72-7.36 (m, 3H), 7.25-7.21 (m,
2H), 7.19-7.15 (m, 1H), 7.08 (dd, 1H, J ) 5.12 an 11.52 Hz),
4.17 (t, 2H, J ) 6.23 Hz), 4.03-3.98 (m, 1H), 3.88-3.82 (m,
2H), 3.59-3.78 (m, 14H), 2.70 (t, 2H, J ) 7.34 Hz), 2.05-1.98
(m, 2H); 13C NMR (100.75 MHz, CDCl3) δ 166.9, 140.6, 134.2,
133.8, 133.4, 131.1, 129.9, 129.7, 128.7, 128.7, 126.4, 77.1, 71.3,
71.0, 70.9, 70.8, 70.5, 70.2, 66.0, 31.6, 30.7; HRMS (EI) [M +
Na]+: calcd for C25H32O9SNa 531.1659, found 531.1673.
(Chlorosulfonyl)benzoate (1g): (0.51 g, 37%); IR (neat) 1739
1
(CdO), 1366, 1192 (SO2) cm-1; HNMR (400 MHz, CDCl3) δ
8.16 (dd, 1H, J ) 0.76 and 8.16 Hz), 7.83-7.70 (m, 3H), 4.58
(dd, 1H, J ) 4.17 and 11.62 Hz, 1H), 4.41 (dd, 1H, J ) 5.88
and 11.64 Hz), 4.02-3.96 (m, 1H), 3.87-3.56 (m, 18H);
13CNMR (100.75 MHz, CDCl3) δ 166.0, 141.6, 135.5, 132.5,
131.7, 130.4, 129.2, 77.2, 71.1, 70.9, 70.8, 70.7, 70.6, 70.5, 70.5,
70.3, 70.2, 70.1, 70.1, 69.9, 66.5, 39.4; HRMS (EI) [M + Na]+:
calcd for C18H25ClO8SNa 475.0805, found 475.0852.
Preparation of 3-Phenylpropyl 2-(Methylcarboxy)-1-
benzosulfonate (2a). To a dichloromethane solution (10 mL)
of methyl 2-(chlorosulfonyl) benzoate (0.35 g, 1.5 mmol) was
added DMAP (0.21 g, 1.8 mmol) under argon. The reaction
mixture was cooled to 0 °C before the addition of phenyl
propanol (0.0.5 g, 3.75 mmol). The resulting mixture was
warmed to room temperature and stirred for 1 h. The solvent
was evaporated in vacuo. The sulfonate ester 3a was purified
by flash chromatography. Elution with a hexane/acetone (85:
15 v/v) mixture yielded a gummy material in 41% (0.4 g) yield.
3-Phenylpropyl [2-Methyl-(1,4,7,10,13-pentaoxocyclo-
pentadecylcarboxy)]-1-benzosulfonate (3b): (0.2 g, 39%);
IR (neat) 1725 (CdO), 1357, 1196 (SO2) cm-1 1HNMR (400
;
IR (neat): 1737 (CO), 1355, 1170 (SO2) cm-1 1HNMR (400
;
MHz, CDCl3) δ 7.96 (d, 1H, J ) 7.87 Hz), 7.69-7.57 (m, 3H),
7.22-7.05 (m, 5H), 4.50 (dd, 1H, J ) 4.31 and 11.43 Hz), 4.35
(dd, 1H, J ) 5.79 and 11.59 Hz), 4.13 (t, J ) 6.19 Hz, 2H),
3.96-3.91 (m, 1H), 3.83-3.54 (m, 18H), 2.66 (t, 2H, J ) 7.45
Hz), 2.01-1.94 (m, 2H); 13C NMR (100.75 MHz, CDCl3) δ 166.9,
140.6, 133.7, 133.5, 131.0, 129.9, 129.8, 128.7, 128.6, 126.3,
79.8, 71.6, 71.2, 71.2, 71.0, 70.9, 70.9, 70.7, 70.6, 70.6, 70.4,
70.1, 66.2, 63.1, 31.6, 30.7; HRMS (EI) [M + Na]+: calcd for
C27H36O10SNa 575.1921, found 575.1927.
MHz, CDCl3) δ 8.00 (dd, J ) 1.0 and 7.7 Hz), 7.72-7.59 (m,
3H), 7.26-7.15 (m, 3H), 7.10-1.08 (m, 2H), 4.16 (t, J ) 6.2
Hz, 2H), 2.69 (t, J ) 7.34 Hz, 2H), 2.05-1.98 (m, 2H), 3.96 (s,
3H); 13CNMR (100.75 MHz, CDCl3) δ 167.5, 140.5, 134.32,
133.7, 133.5, 131.0, 130.0, 129.6, 128.7, 128.6, 126.3, 70.7, 53.5,
31.6, 30.8; HRMS (EI) [M + H]+: calcd for C17H19ClO5S
335.0975, found 335.0940.
Representative Procedure: Preparation of 3-Phenyl-
propyl 2-(2-Oxobutylcarboxy)-1-benzosulfonate (2b). To
a dichloromethane solution (10 mL) of 1b (0.536 g, 1.92 mmol)
was added DMAP (0.25 g, 2.08 mmol) under argon. The
reaction mixture was cooled to 0 °C before the addition of
phenylpropanol (0.47 g, 3.48 mmol). The resulting mixture was
warmed to room temperature and stirred for 1 h. The solvent
was evaporated in vacuo. The crude sulfonate ester was then
purified by flash chromatography by eluting with hexane/
acetone (70:30 v/v) to give 2a as a gummy material (0.45 g,
1-Phenyl-2-propyl 2-(2,5-dioxoheptylcarboxy)-1-ben-
zosulfonate (4a): (0.62 g, 93%); IR (neat) 1734 (CdO), 1355,
1176 (SO2) cm-1; 1H NMR (400 MHz, CDCl3 δ 7.78 (d, J ) 7.9
Hz, 1H), 7.60-7.59 (m, 2H), 7.50-7.45 (m, 1H), 7.19-7.07 (m,
5H), 4.94 (qdd, J ) 6.3, 6.3, 6.7 Hz, 1H), 4.53-4.51 (m, 2H),
3.84-3.81 (m, 2H), 3.67-3.64 (m, 2H), 3.55-3.52 (m, 2H), 3.61
(s, 3H), 3.00 (dd, J ) 6.3, 13.7 Hz, 1H), 2.82 (dd, J ) 6.8, 13.7,
1H), 1.32 (d, J ) 6.2 Hz, 3H); 13CNMR (100.75 MHz, CDCl3)
δ 167.1, 136.3, 135.1, 133.3, 131.1, 130.9, 129.7, 129.5, 129.4,
128.6, 126.9, 82.2, 72.0, 70.65, 68.9, 65.5, 59.2, 43.0, 20.7;
HRMS (EI) [M + H]+: calcd for C21H27O7S 423.1477, found
423.1485.
1
72%); IR (neat) 1739 (CdO), 1369, 1196 (SO2) cm-1; HNMR
(400 MHz, CDCl3) δ 7.98 (dt, 1H, J ) 0.7 and 7.8 Hz), 7.69-
7.67 (m, 2H), 7.64-7.58 (m, 1H), 7.24-7.13 (m, 3H), 7.08 (d,
2H, J ) 6.84 Hz), 4.52-4.49 (m, 2H), 4.16 (t, 2H, J ) 6.2 Hz),
3.73-3.70 (m, 2H), 3.37 (s, 3H), 2.7 (t, 2H, J ) 7.3 Hz), 2.04-
1.97 (m, 2H); HRMS (EI) [M + H]+: calcd for C19H23O6SNa
401.1035, found 401.1040.
4-Decyl 2-(2,5-Dioxoheptylcarboxy)-1-benzosulfonate
(4b): (0.61 g, 96%); IR (neat) 1732 (CdO), 1365, 1156 (SO2)
1
cm-1; HNMR (400 MHz, CDCl3) δ 8.00 (d, J ) 7.5 Hz, 1H),
7.67-7.58 (m, 3H), 4.72 (tt, J ) 6.1, 6.0 Hz, 1H), 4.53-4.50
(m, 2H), 3.84-3.81 (m, 2H), 3.67-3.65 (m, 2H), 3.55-3.53 (m,
2H), 3.36 (s, 3H), 1.65-1.5 (m, 5H), 1.36-1.09 (m, 9H), 0.84
(t, J ) 6.6 Hz, 3H), 0.82 (t, J ) 7.4, 3H); 13CNMR (100.75 MHz,
CDCl3) δ 167.1, 135.7, 133.3, 130.7, 129.6, 129.4, 86.0, 72.0,
70.6, 68.9, 65.4, 59.2, 36.4, 34.3, 31.7, 29.1, 22.1, 18.1, 14.2,
14.0; HRMS (EI) [M + H]+: calcd for C22H37O7S 445.2260,
found (M + H)+ 445.2263.
3-Phenylpropyl 2-(2,5-Dioxoheptylcarboxy)-1-benzo-
sulfonate (2c): (0.6 g, 95%); IR (neat) 1733 (CdO), 1350, 1166
1
(SO2) cm-1; HNMR (400 MHz, CDCl3) δ 7.98 (d, J ) 7.3 Hz,
1H), 7.70-7.68 (m, 2H), 7.63-7.58 (m, 1H), 7.24-7.07 (m, 5H),
4.54-4.52 (m, 2H), 4.16 (t, J ) 6.2 Hz, 2H), 3.84-3.82 (m, 2H),
3.66-3.63 (m, 2H), 3.53-3.51 (m, 2H), 3.55 (s, 3H), 2.69 (t, J
) 7.3 Hz), 1.97-2.04 (m, 2H); 13C NMR (100.75 MHz, CDCl3)
δ 167.0, 140.6, 134.1, 133.7, 133.5, 131.0, 129.9, 129.8, 128.6,
128.6, 126.3, 72.0, 70.8, 70.6, 68.9, 65.5, 59.2, 31.5, 30.7; HRMS
(EI) [M + H]+: calcd for C21H27O7S 423.1477, found 423.1469.
Synthesis of 2-Adamantyl 2-(2,5-Dioxoheptylcarboxy)-
1-benzosulfonate (4c). To a pyridine solution (10 mL) of 1
(0.9 g, 2.8 mmol) was added 2-adamantanol (0.85 g, 5.5 mmol)
at 0 °C. The reaction mixture was slowly warmed to room
temperature and allowed to stir for 16 h. The pyridine was
removed in vacuo, resulting in a gummy material. The crude
material was purified by flash chromatography by elution with
a hexane/acetone (70:30 v/v) to give 6 (1.18 g, 96%) as a gummy
3-Phenylpropyl 2-(2,5,8-Trioxodecylcarboxy)-1-benzo-
sulfonate (2d): (0.7 g, 87%); IR (neat) 1736 (CdO), 1369, 1196
(SO2) cm-1; 1HNMR (400 MHz, CDCl3) δ 8.01 (dt, 1H, J ) 0.83
and 7.83 Hz), 7.69 (dt, 2H, J ) 0.96 and 4.87 Hz), 7.65-7.60
(m, 1H), 7.26-7.21 (m, 2H), 7.19-7.15 (m, 1H), 7.10-7.08 (m,
2H), 4.54-4.52 (m, 2H, 4.16 (t, 2H, J ) 6.24 Hz), 3.85-3.82
(m, 2H), 3.69-3.61 (m, 6H), 3.54-3.51 (m, 2H), 3.36 (s, 3H),
2.71 (t, 2H, J ) 7.31 Hz), 2.05-1.98 (m, 2H); 13C NMR (100.75
MHz, CDCl3) δ 167.0, 140.6, 134.1, 133.8, 133.5, 131.0, 130.0,
129.8, 128.7, 126.4, 72.1, 70.9, 70.7, 68.9, 65.6, 59.2, 31.6, 30.7;
HRMS (EI) [M + H]+: calcd for C23H30O8SNa 489.1559, found
489.1561.
material. IR (neat) 1734 (CdO), 1360, 1185 (SO2) cm-1 1H
;
NMR (400 MHz, CDCl3) δ 8.02 (d, J ) 7.4 Hz, 1H), 7.67-7.58
(m, 3H), 4.83 (m, 1H), 4.54-4.51 (m, 2H, 3.67-3.65 (m, 2H),
3.55-3.53 (m, 2H), 3.36 (s, 3H), 2.10-2.03 (m, 4H), 1.83-0.180
(m, 4H), 1.69-1.62 (m, 4H), 1.53-1.50 (m, 2H); 13C NMR
(100.75 MHz, CDCl3) δ 167.0 (CO), 135.34, 133.1, 130.8, 129.7,
129.4, 87.8, 72.0, 70.6, 68.9, 65.4, 59.2, 37.3, 36.5, 32.9, 31.3,
27.0, 24.7; HRMS (EI) [(M + 2H) - C10H15]+: calcd for
C12H17O7S 305.0695, found 305.0699.
3-Phenylpropyl 2-(2,5,8,11-Tetraoxotridecylcarboxy)-
1-benzosulfonate (2e): (0.75 g, 83%); IR (neat) 1728 (CdO),
1
1371, 1197 (SO2) cm-1; HNMR (400 MHz, CDCl3) δ 8.00 (dt,
Representative Procedure: Reaction of NALG Sul-
fonate 2c with NaBr. Aryl sulfonate ester 2c (0.42 g, 1.00
mmol) was dissolved in acetone, and NaBr (0.4 g, 4.0 mmol)
1H, J ) 0.82 and 7.84 Hz), 7.70-7.69 (m, 2H), 7.64-7.59 (m,
1H), 7.25-7.08 (m, 5H0, 4.53-4.51 (m, 2H), 3.67-3.61 (m,
8120 J. Org. Chem., Vol. 70, No. 20, 2005