P. Passacantilli, G. Piancatelli et al.
FULL PAPER
General Procedure for the Preparation of Compounds 15a,b, 19, and
23a–d: CH3SO2Cl (1.2 equiv.) was added at 0 °C to a stirred solu-
tion of the appropriate alcohol (1 equiv.) in dry pyridine (11 mL/
mmol) and NEt3 (3 mL/mmol). The reaction mixture was stirred
at room temp. overnight and after that time TLC (hexanes/Et2O,
7:3) showed the disappearance of the starting material. The reac-
tion mixture was then diluted with Et2O (200 mL/mmol), washed
in a separating funnel with H2O (until neutrality) and then brine
(20 mL/mmol), dried with anhydrous Na2SO4, and the solvent re-
moved under reduced pressure. The residue was then purified by
column chromatography.
CH2Ph), 4.02–3.48 (m, 9 H, 4-H, 6-HA, 6-HB, 2Ј-H, 3Ј-H, 4Ј-H, 5Ј-
H, 6Ј-HA, 6Ј-HB), 2.92 (s, 3 H, CH3SO2), 2.11–1.69 (m, 2 H, 5-HA,
5-HB), 0.94 [s, 9 H, C(CH3)3], 0.09 (s, 6 H, 2 CH3) ppm. 13C NMR:
δ = 138.6, 138.4, 138.3, 137.9, 137.6 (Cquat, Ph), 128.2, 128.0, 127.8,
127.7, 127.6, 127.4, 127.3 (Ph), 103.2 (C-1Ј), 83.4, 82.4, 79.4, 78.0,
75.7, 73.8, 73.2 (C-2, C-3, C-4, C-2Ј, C-3Ј, C-4Ј, C-5Ј), 74.9, 74.8,
74.6, 73.4, 72.8, 72.0 (CH2Ph), 69.3, 68.3 (C-1, C-6Ј), 59.5 (C-6),
38.3 (CH3SO2), 33.1 (C-5), 25.9 [SiC(CH3)3], 18.1 [SiC(CH3)3], –5.3
[Si(CH3)2] ppm. HRMS: calcd. for C61H76O12SSi 1083.4724 [M +
Na]+; found 1083.4775.
Silyl Ether 23b: This compound was prepared from 22b (100 mg,
0.10 mmol) through the general procedure described above, puri-
fied by column chromatography (SiO2; hexanes/EtOAc, 8:2), and
obtained as a viscous oil (91 mg, 0.08 mmol, 85%). [α]D = +22.0 (c
Silyl Ether 15a: This compound was prepared from 14a (100 mg,
0.18 mmol) through the general procedure described above, puri-
fied by column chromatography (SiO2; hexanes/Et2O, 8:2), and ob-
tained as a viscous oil (102 mg, 0.16 mmol, 90%). [α]D = +10.5 (c
= 1.1, CHCl ). IR (CHCl ): ν = 2990, 2980, 2950, 1600, 1500, 1450,
˜
3
3
1300, 1250, 1082 cm–1. 1H NMR: δ = 7.43–7.20 (m, 30 H, Ph),
5.00–5.05 (m, 1 H, 2-H), 5.01–4.12 (m, 15 H, 1Ј-H, 1-HA, 1-HB, 6
CH2Ph), 4.08–3.39 (m, 10 H, 3-H, 4-H, 6-HA, 6-HB, 2Ј-H, 3Ј-H,
4Ј-H, 5Ј-H, 6Ј-HA, 6Ј-HB), 2.93 (s, 3 H, CH3SO2), 2.14–1.79 (m, 2
H, 5-HA, 5-HB), 0.95 [s, 9 H, C(CH3)3], 0.09 (s, 6 H, 2 CH3) ppm.
13C NMR: δ = 138.6, 138.4, 138.3, 138.1, 137.9, 137.6 (Cquat, Ph),
128.2, 127.9, 127.7, 127.5, 127.3, 127.2 (Ph), 102.2 (C-1Ј), 84.7,
83.0, 82.2, 77.8, 77.5, 77.6, 74.8 (C-2, C-3, C-4, C-2Ј, C-3Ј, C-4Ј,
C-5Ј), 75.5, 74.7, 74.6, 73.4, 72.9, 72.0 (CH2Ph), 69.1, 68.8 (C-1,
C-6Ј), 59.5 (C-6), 38.4 (CH3SO2), 33.1 (C-5), 25.9 [SiC(CH3)3], 17.9
[SiC(CH3)3], –5.3 [Si(CH3)2] ppm. HRMS: calcd. for C61H76O12SSi
1083.4724 [M + Na]+; found 1083.4695.
= 1.1, CHCl ). IR (CHCl ): ν = 3000, 2970, 2950, 1600, 1500, 1480,
˜
3
3
1300, 1278, 1082 cm–1. 1H NMR: δ = 7.44–7.28 (m, 15 H, Ph),
5.10–5.03 (m, 1 H, 2-H), 4.87–4.56 (m, 6 H, 3 CH2Ph), 4.07–3.47
(m, 6 H, 1-HA, 1-HB, 3-H, 4-H, 6-HA, 6-HB), 3.01 (br. s, 3 H,
CH3SO2), 1.93–1.73 (m, 2 H, 5-HA, 5-HB), 0.94 [s, 9 H, C(CH3)3],
0.08 (s, 6 H, 2 CH3) ppm. 13C NMR: δ = 138.0, 137.5, 137.4 (Cquat
,
Ph), 128.2, 128.1, 127.8, 127.5, 127.4 (Ph), 83.1, 80.5, 75.7 (C-2,
C-3, C-4), 74.1, 72.6, 71.7 (CH2Ph), 68.1 (C-1), 58.0 (C-6), 38.2
(CH3SO2), 33.6 (C-5), 25.7 [SiC(CH3)3], 18.0 [SiC(CH3)3], –5.5
[Si(CH3)2] ppm. HRMS: calcd. for C34H48O7SSi 651.2788 [M +
Na]+; found 651.2771.
Silyl Ether 15b: This compound was prepared from 14b (100 mg,
0.18 mmol) through the general procedure described above, puri-
fied by column chromatography (SiO2; hexanes/Et2O, 8:2), and ob-
tained as a viscous oil (102 mg, 0.16 mmol, 90%). [α]D = +14.3 (c
Silyl Ether 23c: This compound was prepared from 22c (100 mg,
0.10 mmol) through the general procedure described above, puri-
fied by column chromatography (SiO2; hexanes/EtOAc, 8:2), and
obtained as a viscous oil (97 mg, 0.09 mmol, 90%). [α]D = +58.7 (c
= 1.1, CHCl ). IR (CHCl ): ν = 2970, 2950, 1600, 1550, 1480, 1300,
˜
3
3
= 1.1, CHCl ). IR (CHCl ): ν = 2990, 2970, 1600, 1500, 1450, 1300,
˜
3
3
1278, 1082 cm–1. 1H NMR: δ = 7.40–7.30 (m, 15 H, Ph), 4.96–4.50
(m, 8 H, 2-H, 3-H, 3 CH2Ph), 4.00–3.91 (m, 1 H, 4-H), 3.85–3.78
(m, 4 H, 1-HA, 1-HB, 6-HA, 6-HB), 2.92 (s, 3 H, CH3SO2), 2.12–
1.68 (m, 2 H, 5-HA, 5-HB), 0.95 [s, 9 H, C(CH3)3], 0.09 (s, 6 H, 2
CH3) ppm. 13C NMR: δ = 138.0, 137.5, 137.4 (Cquat, Ph), 128.2,
128.1, 127.9, 127.5 (Ph), 83.1, 80.5, 75.7 (C-2, C-3, C-4), 74.1, 73.2,
72.7 (CH2Ph), 69.1 (C-1), 59.0 (C-6), 38.2 (CH3SO2), 33.6 (C-5),
24.7 [SiC(CH3)3], 18.0 [SiC(CH3)3], –5.5 [Si(CH3)2] ppm. HRMS:
calcd. for C34H48O7SSi 651.2788 [M + Na]+; found 651.2799.
1250, 1082 cm–1. 1H NMR: δ = 7.45–7.29 (m, 30 H, Ph), 5.18–5.09
(m, 1 H, 2-H), 5.01 (d, J1Ј,2Ј = 3.5 Hz, 1 H, 1Ј-H), 5.04–4.36 (m,
15 H, 1-HA, 1-HB, H-3, 6 CH2Ph), 4.10–3.57 (m, 9 H, 4-H, 6-HA,
6-HB, 2Ј-H, 3Ј-H, 4Ј-H, 5Ј-H, 6Ј-HA, 6Ј-HB), 2.98 (s, 3 H, CH3SO2),
2.08–1.85 (m, 1 H, 5-HA), 1.84–1.62 (m, 1 H, 5-HB), 0.93 [s, 9 H,
C(CH3)3], 0.07 (s, 6 H, 2 CH3) ppm. 13C NMR: δ = 138.6, 138.1,
137.9, 137.5, 137.4 (Cquat, Ph), 128.1, 127.8, 127.6, 127.5, 127.3,
127.2 (Ph), 95.9 (C-1Ј), 82.8, 81.7, 79.7, 77.6, 76.9, 74.5, 70.9 (C-2,
C-3, C-4, C-2Ј, C-3Ј, C-4Ј, C-5Ј), 75.4, 75.1, 73.5, 73.2, 73.0, 72.4
(CH2Ph), 69.3, 68.2 (C-1, C-6Ј), 59.8 (C-6), 38.3 (CH3SO2), 33.6
(C-5), 25.8 [SiC(CH3)3], 18.1 [SiC(CH3)3], –5.5 [Si(CH3)2] ppm.
HRMS: calcd. for C61H76O12SSi 1083.4724 [M + Na]+; found
1083.4750.
Silyl Ether 19: This compound was prepared from 18 (100 mg,
0.22 mmol) through the general procedure described above, puri-
fied by column chromatography (SiO2; hexanes/Et2O, 8:2), and ob-
tained as a viscous oil (105 mg, 0.20 mmol, 90%). [α]D = –27.8 (c
= 1.1, CHCl ). IR (CHCl ): ν = 2980, 2970, 1600, 1550, 1480, 1300,
˜
3
3
Silyl Ether 23d: This compound was prepared from 22d (100 mg,
0.10 mmol) through the general procedure described above, puri-
fied by column chromatography (SiO2; hexanes/EtOAc, 8:2), and
obtained as a viscous oil (97 mg, 0.09 mmol, 90%). [α]D = +42.2 (c
1278, 1082 cm–1. H NMR: δ = 7.42–7.25 (m, 10 H, Ph), 5.02 (qd,
J2,1 = 7.0, J2,3 = 1.9 Hz, 1 H, 2-H), 4.86–4.51 (m, 4 H, 2 CH2Ph),
3.90–3.59 (m, 4 H, 3-H, 4-H, 6-HA, 6-HB), 2.92 (s, 3 H, CH3SO2),
1.96–1.61 (m, 2 H, 5-HA, 5-HB), 1.51 (d, J1,2 = 7.0 Hz, 3 H, 1-HA,
1-HB, 1-HC), 0.93 [s, 9 H, C(CH3)3], 0.09 (s, 6 H, 2 CH3) ppm. 13C
NMR: δ = 138.4, 138.2 (Cquat, Ph), 128.4, 127.8, 127.6, 127.2, 127.1
(Ph), 82.2, 79.8, 75.9 (C-2, C-3, C-4), 74.2, 73.3 (CH2Ph), 59.2 (C-
6), 38.6 (CH3SO2), 34.2 (C-5), 26.0 [SiC(CH3)3], 19.8 [SiC(CH3)3],
16.7 (C-1), –5.2 [Si(CH3)2] ppm. HRMS: calcd. for C27H42O6SSi
545.2369 [M + Na]+; found 545.2345.
1
= 1.1, CHCl ). IR (CHCl ): ν = 2980, 2950, 1600, 1500, 1400, 1300,
˜
3
3
1250, 1082 cm–1. 1H NMR: δ = 7.45–7.29 (m, 30 H, Ph), 5.08–4.34
(m, 17 H, 1-HA, 1-HB, 2-H, 3-H, 1Ј-H, 6 CH2Ph), 4.18–3.50 (m, 9
H, 4-H, 6-HA, 6-HB, 2Ј-H, 3Ј-H, 4Ј-H, 5Ј-H, 6Ј-HA, 6Ј-HB), 2.82
(s, 3 H, CH3SO2), 2.05–1.81 (m, 2 H, 5-HA, 5-HB), 0.94 [s, 9 H,
C(CH3)3], 0.08 (s, 6 H, 2 CH3) ppm. 13C NMR: δ = 138.8, 138.5,
138.3, 138.1, 137.9 (Cquat, Ph), 128.2, 128.0, 127.8, 127.7, 127.4
(Ph), 97.6 (C-1Ј), 82.8, 80.7, 78.2, 76.2, 75.6, 74.6, 69.6 (C-2, C-3,
C-4, C-2Ј, C-3Ј, C-4Ј, C-5Ј), 74.7, 74.2, 73.3, 72.7, 72.2 (CH2Ph),
68.7 (C-6Ј), 66.1 (C-1), 59.4 (C-6), 38.1 (CH3SO2), 33.6 (C-5), 25.8
[SiC(CH3)3], 18.1 [SiC(CH3)3], –5.4 [Si(CH3)2] ppm. HRMS: calcd.
for C61H76O12SSi 1083.4724 [M + Na]+; found 1083.4766.
Silyl Ether 23a: This compound was prepared from 22a (100 mg,
0.10 mmol) through the general procedure described above, puri-
fied by column chromatography (SiO2; hexanes/Et2O, 8:2), and ob-
tained as a viscous oil (97 mg, 0.09 mmol, 90%). [α]D = +8.5 (c =
1.1, CHCl ). IR (CHCl ): ν = 3000, 2970, 1600, 1500, 1400, 1300,
˜
3
3
1250, 1082 cm–1. 1H NMR: δ = 7.45–7.27 (m, 30 H, Ph), 5.18–5.09
General Procedure for the Preparation of Compounds 16a,b, 20, and
(m, 1 H, 2-H), 5.03–4.06 (m, 16 H, 1Ј-H, 1-HA, 1-HB, 3-H, 6 24a–d: TBAF (1 equiv.) was added at room temp. to a stirred solu-
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Eur. J. Org. Chem. 2007, 1463–1473