C. Jin et al. / Tetrahedron 58 12002) 3737±3746
3743
2H), 2.02±1.72 4m, 4H), 1.44 4s, 9H); 13C NMR450 MHz,
CDCl3) d 169.4, 140.7, 139.2, 133.5, 129.2, 128.6, 128.0,
126.6, 81.3, 65.9, 55.7, 36.3, 28.0, 19.4. Anal. calcd for
C22H28O5S: C, 65.32; H, 6.98. Found: C, 65.41; H, 6.93.
Anal. calcd for C13H16O4S: C, 58.19; H, 6.02. Found: C,
58.54; H, 6.13.
4.3.5. 4-Benzenesulfonyl-7-phenyl-oxepan-3-one /4e).
White solid; 85% yield 4mixture of diastereomers); mp
145.0±146.58C; IR4KBr) 3058, 2911, 1720, 1585,
1
1447 cm21; H NMR4200 MHz, CDCl ) d 8.11±7.20 4m,
4.3. General procedure for the intramolecular acylation
of tert-butyl esters 2a±e
3
10H), 4.76 4dd, J11.0, 2.5 Hz, 1H), 4.42±3.98 4m, 3H),
2.80±2.68 4m, 1H), 2.34±1.82 4m, 3H); 13C NMR450 MHz,
CDCl3) d 204.0, 141.4, 138.1, 134.0, 129.8, 128.9,
128.6, 128.0, 125.4, 85.3, 76.9, 72.7, 36.5, 28.1, 24.3.
Anal. calcd for C18H18O4S: C, 65.44; H, 5.50. Found: C,
65.15; H, 5.73.
4.3.1. 4-Benzenesulfonyl-6-methyl-dihydropyran-3-one
/4a). To a solution of 2a 4328 mg, 1.00 mmol) in THF
430 mL) at 2788C under N2 was added LHMDS
42.00 mL, 2.00 mmol) slowly and the mixture was stirred
for 4 h. The reaction was quenched with saturated NH4Cl
42 mL). The THF was removed in vacuo and the residue was
dissolved in CH2Cl2 4100 mL), washed with brine 450 mL),
dried 4Na2SO4) and the solvent was removed in vacuo. The
crude product was puri®ed by ¯ash silica gel chromato-
graphy 415±25% EtOAc±hexane) to give a diastereomeric
mixture 4a 4220 mg, 87%) as a colorless oil: IR4neat) 3452,
4.3.6. 1-/3-Benzenesulfonyl-1-methyl-propoxy)-butan-2-
ol /5a). To a solution of 1a 42.14 g, 10.0 mmol) in THF
45 mL) at room temperature under N2 was added potassium
tert-butoxide 40.12 g, 1.00 mmol) followed by 1,2-epoxy-
butane 42.58 mL, 30.0 mmol), and the mixture was stirred
at 608C for 2 d. The reaction mixture was cooled to room
temperature and poured into ice-water 420 mL). The crude
product was extracted into EtOAc 4100 mL), washed with
1N HCl 43£30 mL), NaHCO3 43£30 mL), brine 430 mL)
and dried 4Na2SO4). The solvent was removed in vacuo.
The crude product was puri®ed by ¯ash silica gel chromato-
graphy 425±50% EtOAc±hexane) to give 5a 42.45 g, 86%)
1
3067, 2977, 1747, 1585, 1447 cm21; H NMR4200 MHz,
CDCl3) d 8.05±7.50 4m, 5H), 4.45±3.58 4m, 4H), 2.95±2.80
4m, 0.45H), 2.65±2.50 4m, 0.35H), 2.32±2.10 4m, 1H),
1.98±1.70 4m, 0.20H); 1.40±1.15 4m, 3H); 13C NMR
450 MHz, CDCl3) d 198.0, 161.4, 139.5, 138.2, 137.5,
134.4, 134.1, 133.7, 129.2, 128.7, 127.1, 102.1, 73.8, 71.7,
71.0, 69.3, 68.6, 68.2, 65.5, 32.9, 32.6, 20.9, 20.5. Anal.
calcd for C12H14O4S: C, 56.68; H, 5.55. Found: C, 56.61;
H, 5.46.
as a colorless oil: IR4neat) 3511, 3061, 2977, 1585,
1447 cm21; H NMR4200 MHz, CDCl ) d 8.02±7.50 4m,
1
3
5H), 4.72±3.10 4m, 6H), 2.37 4br, 1H), 2.10±1.70 4m, 2H),
1.44 4quintet, J7.1 Hz, 2H), 1.13 4d, J6.2 Hz, 3H), 0.94
4.3.2. 4-Benzenesulfonyl-6-trityloxymethyl-dihydro-
pyran-3-one /4b). White solid; 99% yield 4mixture of
diastereomers); mp 49.0±54.08C; IR4KBr) 3433, 3061,
4t, J7.5 Hz, 3H); 13C NMR450 MHz, CDCl ) d 139.3,
3
133.7, 129.3, 128.0, 73.4, 72.4, 71.7, 52.6, 29.4, 26.1,
19.3, 9.9. Anal. calcd for C14H22O4S: C, 58.72; H, 7.74.
Found: C, 58.97; H, 7.73.
1
2923, 1732, 1642 cm21; H NMR4200 MHz, CDCl ) d
3
8.03±7.20 4m, 20H), 4.50±3.65 4m, 4H), 3.40±2.97 4m,
2H), 2.89±1.90 4m, 2H); 13C NMR450 MHz, CDCl ) d
4.3.7. 1-/4-Benzenesulfonyl-1-methyl-butoxy)-butan-2-ol
/5b). To a solution of 1d 41.11 g, 4.80 mmol) in THF 45 mL)
at room temperature under N2 was added potassium tert-
butoxide 40.06 g, 0.48 mmol) followed by 1,2-epoxybutane
41.24 mL, 14.4 mmol), and the mixture was stirred at 608C
for 2 d. The reaction mixture was cooled to room tempera-
ture and poured into ice-water 420 mL). The crude product
was extracted into EtOAc 4100 mL), washed with 1N HCl
43£30 mL), NaHCO3 43£30 mL), brine 430 mL) and dried
4Na2SO4). The solvent was removed in vacuo. The crude
product was puri®ed by ¯ash silica gel chromatography
425±50% EtOAc±hexane) to give 5b 40.53 g, 36%) as a
3
198.1, 161.5, 143.7, 143.6, 139.7, 138.3, 134.3, 134.1,
133.6, 129.6, 129.3, 129.2, 129.0, 128.7, 127.9,
127.8, 127.3, 127.1, 102.1, 86.8, 86.7, 74.4, 74.3, 73.8,
72.3, 68.4, 68.2, 65.7, 65.5, 29.7, 28.1, 27.9, 25.0. Anal.
calcd for C31H28O5S: C, 72.63; H, 5.51. Found: C, 72.23;
H, 5.67.
4.3.3. 4-Benzenesulfonyl-6-phenyl-dihydropyran-3-one
/4c). White solid; 99% yield 4mixture of diastereomers);
mp 96.5±98.08C; IR4KBr) 3455, 3064, 2926, 1729, 1642,
1585, 1447 cm21; 1H NMR4200 MHz, CDCl 3) d 8.10±7.15
4m, 10H), 5.42±5.28 4m, 0.40H), 4.85±3.97 4m, 3.60H),
colorless oil: IR4neat) 3508, 3061, 2969, 1585,
1447 cm21; H NMR4200 MHz, CDCl ) d 8.05±7.40 4m,
3.20±2.15 4m, 2H); 13C NMR450 MHz, CDCl ) d 197.4,
1
3
3
161.4, 139.8, 139.5, 137.5, 134.5, 134.3, 133.7, 129.3,
128.9, 128.5, 127.3, 125.7, 102.5, 74.8, 74.3, 69.0, 66.0,
33.3, 29.6. Anal. calcd for C17H16O4S: C, 64.54; H, 5.10.
Found: C, 64.51; H, 4.97.
5H), 3.52±2.92 4m, 6H), 2.28 4br, 1H), 1.95±1.65 4m, 2H),
1.60±1.30 4m, 4H), 1.12 4d, J5.9 Hz, 3H), 0.95
4t, J7.5 Hz, 3H); 13C NMR450 MHz, CDCl 3) d
139.3, 133.6, 129.3, 128.0, 75.2, 75.0, 72.5, 72.4, 72.1,
71.8, 56.2, 35.0, 26.3, 26.2, 19.5, 19.4, 19.0, 9.9. Anal.
calcd for C15H24O4S: C, 59.97; H, 8.05. Found: C, 60.28;
H, 7.87.
4.3.4. 4-Benzenesulfonyl-7-methyl-oxepan-3-one /4d).
White solid; 57% yield 4mixture of diastereomers); mp
110.0±111.08C; IR4KBr) 3064, 2920, 1717, 1585,
1
1450 cm21; H NMR4200 MHz, CDCl ) d 8.10±7.50 4m,
4.3.8. 4-/3-Benzenesulfonyl-1-methyl-propoxy)-butan-2-
one /6a). To a suspension of 5a 4350 mg, 1.21 mmol) and
Ê
powdered 4 A molecular sieves 4610 mg) in CH2Cl2
42.4 mL) at room temperature under N2 was added
4-methylmorpholine N-oxide 4210 mg, 1.82 mmol)
followed by TPAP 422.0 mg, 5 mol%), and the mixture
3
5H), 4.70±7.54 4m, 1H), 4.20 4d, J18.1 Hz, 1H), 3.90 4d,
J18.1 Hz, 1H), 3.48±3.30 4m, 1H), 2.70±2.55 4m, 1H),
2.08±1.68 4m, 3H), 1.24 4d, J6.2 Hz, 3H); 13C NMR
450 MHz, CDCl3) d 204.3, 138.3, 138.1, 134.0, 129.6,
128.9, 80.0, 72.4, 72.0, 35.8, 31.8, 23.9, 22.2, 21.8, 20.0.