ACCEPTED MANUSCRIPT
Tetrahedron
5
(0.5 mmol) in a co-solvent of THF (5 mL) and MeOH (5
128.95 (2x), 126.84 (2x), 78.19, 72.09, 71.72, 68.69, 21.60,
21.06, 17.49.
o
mL) at 0 C. The reaction mixture was stirred for 1 h at 0
oC and the solvent was concentrated. The residue was
diluted with water (10 mL) and the mixture was extracted
with CH2Cl2 (3 x 20 mL). The combined organic layers
were washed with brine, dried, filtered and evaporated to
afford crude product. Purification on silica gel
(hexanes/EtOAc = 8/1~3/1) afforded 5.
4.2.5. 1-Biphenyl-4-yl-2-(toluene-4sulfonyl)pent-4-yn-1-ol
(5e). Yield = 93% (181 mg); Colorless solid; mp = 142-
o
143 C (recrystallized from hexanes and EtOAc); HRMS
(ESI, M++1) calcd for C24H23O3S 391.1368, found
1
391.1371; H NMR (400 MHz, CDCl3): δ 7.79 (d, J = 8.4
Hz, 2H), 7.57-7.51 (m, 4H), 7.46-7.42 (m, 4H), 7.38-7.33
(m, 1H), 7.31 (d, J = 8.0 Hz, 2H), 5.35 (d, J = 8.0 Hz, 1H),
4.25 (br s, 1H), 3.59-3.54 (m, 1H), 2.61 (ddd, J = 2.8, 5.2,
18.0 Hz, 1H), 2.44 (s, 3H), 2.44 (ddd, J = 2.8, 5.2, 18.0 Hz,
1H), 1.89 (t, J = 2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
δ 145.19, 141.34, 140.40, 138.31, 135.42, 129.71 (2x),
128.90 (2x), 128.74 (2x), 127.44, 127.32 (2x), 127.20 (2x),
126.97 (2x), 78.20, 71.97, 71.91, 68.55, 21.60, 17.47.
4.2.1. 1-Phenyl-2-(toluene-4-sulfonyl)pent-4-yn-1-ol (5a).
o
Yield = 92% (144 mg); Colorless solid; mp = 152-153 C
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C18H19O3S 315.1055, found 315.1058; H
NMR (400 MHz, CDCl3): δ 7.81 (d, J = 8.4 Hz, 2H), 7.39-
7.29 (m, 7H), 5.27 (d, J = 8.4 Hz, 1H), 4.20 (br s, 1H),
3.52-3.47 (m, 1H), 2.50 (ddd, J = 2.8, 5.2, 18.0 Hz, 1H),
2.45 (s, 3H), 2.29 (ddd, J = 2.8, 5.2, 18.0 Hz, 1H), 1.83 (t,
J = 2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 145.28,
139.31, 135.35, 129.76 (2x), 129.00 (2x), 128.59 (3x),
127.03 (2x), 78.11, 72.35, 71.79, 68.72, 21.66, 17.57.
4.2.6. 1-Naphthalen-2-yl-2-(toluene-4-sulfonyl)pent-4-yn-
1-ol (5f). Yield = 95% (173 mg); Colorless solid; mp =
124-125 oC (recrystallized from hexanes and EtOAc);
HRMS (ESI, M++1) calcd for C22H21O3S 365.1212, found
1
4.2.2. 1-(4-Methoxyphenyl)-2-(toluene-4-sulfonyl)pent-4-
yn-1-ol (5b). Yield = 94% (162 mg); Colorless gum;
HRMS (ESI, M++1) calcd for C19H21O4S 345.1161, found
365.1215; H NMR (400 MHz, CDCl3): δ 7.82-7.73 (m,
6H), 7.50-7.46 (m, 2H), 7.44 (dd, J = 1.6, 8.4 Hz, 1H),
7.21 (d, J = 8.4 Hz, 2H), 5.47 (d, J = 8.0 Hz, 1H), 4.30 (br
s, 1H), 3.66-3.61 (m, 1H), 2.60 (ddd, J = 2.8, 5.2, 18.0 Hz,
1H), 2.41 (ddd, J = 2.8, 5.2, 18.0 Hz, 1H), 2.37 (s, 3H),
1.86 (t, J = 2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
145.18, 136.60, 135.38, 133.29, 132.98, 129.62 (2x),
128.86 (2x), 128.52, 128.05, 127.57, 126.50, 126.32 (2x),
123.95, 78.26, 72.32, 71.91, 68.40, 21.56, 17.45.
1
345.1168; H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.8
Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H),
6.78 (d, J = 8.8 Hz, 2H), 5.18 (d, J = 8.4 Hz, 1H), 3.760 (br
s, 1H), 3.71 (s, 3H), 3.46-3.42 (m, 1H), 2.47 (ddd, J = 2.8,
5.2, 18.0 Hz, 1H), 2.39 (s, 3H), 2.20 (ddd, J = 2.8, 5.2,
18.0 Hz, 1H), 1.85 (t, J = 2.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ 159.41, 144.88, 135.38, 131.40, 129.44 (2x),
128.75 (2x), 128.02 (2x), 113.65 (2x), 78.08, 71.65, 71.62,
68.53, 54.96, 21.38, 17.25.
4.2.7. 2-Benzenesulfonyl-1-(4-methoxyphenyl)pent-4-yn-1-
ol (5g). Yield = 94% (155 mg); Colorless gum; HRMS
(ESI, M++1) calcd for C18H19O4S 331.1004, found
1
4.2.3. 1-(4-Fluorophenyl)-2-(toluene-4-sulfonyl)pent-4-yn-
1-ol (5c). Yield = 93% (154 mg); Colorless solid; mp =
130-131 oC (recrystallized from hexanes and EtOAc);
HRMS (ESI, M++1) calcd for C18H18FO3S 333.0961, found
331.1002; H NMR (400 MHz, CDCl3): δ 7.94-7.91 (m,
2H), 7.65-7.61 (m, 1H), 7.53-7.49 (m, 2H), 7.26 (d, J = 8.4
Hz, 2H), 6.81 (d, J = 8.8 Hz, 2H), 5.22 (d, J = 8.4 Hz, 1H),
3.75 (s, 3H), 3.70 (br s, 1H), 3.51-3.46 (m, 1H), 2.51 (ddd,
J = 2.8, 5.2, 18.0 Hz, 1H), 2.25 (ddd, J = 2.8, 5.2, 18.0 Hz,
1H), 1.83 (t, J = 2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
δ 159.58, 138.55, 133.89, 131.36, 128.93 (2x), 128.84 (2x),
128.10 (2x), 113.83 (2x), 78.03, 71.75, 71.73, 68.70, 55.11,
17.36.
1
333.0963 H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.4
Hz, 2H), 7.39-7.34 (m, 4H), 7.03-6.97 (m, 2H), 5.27 (d, J =
8.4 Hz, 1H), 4.40 (br s, 1H), 3.46-3.41 (m, 1H), 2.49 (ddd,
J = 2.8, 5.2, 18.0 Hz, 1H), 2.46 (s, 3H), 2.29 (ddd, J = 2.8,
5.2, 18.0 Hz, 1H), 1.82 (t, J = 2.8 Hz, 1H); 13C NMR (100
MHz, CDCl3): δ 162.75 (d, J = 245.6 Hz), 145.48, 135.17,
135.08, 129.85 (2x), 128.99 (2x), 128.82 (d, J = 8.3 Hz,
2x), 115.48 (d, J = 22.0 Hz, 2x), 77.91, 71.88, 71.70, 68.65,
21.66, 17.51.
4.2.8. 2-Benzenesulfonyl-1-(4-fluorophenyl)pent-4-yn-1-ol
(5h). Yield = 91% (145 mg); Colorless solid; mp = 146-
o
147 C (recrystallized from hexanes and EtOAc); HRMS
(ESI, M++1) calcd for C17H16FO3S 319.0804, found
1
4.2.4. 2-(Toluene-4-sulfonyl)-1-p-tolylpent-4-yn-1-ol (5d).
319.0807; H NMR (400 MHz, CDCl3): δ 7.94-7.91 (m,
o
Yield = 95% (156 mg); Colorless solid; mp = 74-75 C
2H), 7.70-7.65 (m, 1H), 7.58-7.53 (m, 2H), 7.38-7.34 (m,
2H), 7.02-6.97 (m, 2H), 5.29 (d, J = 8.4 Hz, 1H), 4.20 (br s,
1H), 3.50-3.45 (m, 1H), 2.53 (ddd, J = 2.8, 5.2, 18.0 Hz,
1H), 2.32 (ddd, J = 2.8, 5.2, 18.0 Hz, 1H), 1.82 (t, J = 2.8
Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 162.74 (d, J =
245.6 Hz), 138.28, 135.10 (d, J = 3.8 Hz), 134.21, 129.19
(2x), 128.94 (2x), 128.78 (d, J = 8.4 Hz, 2x), 115.52 (d, J =
21.2 Hz, 2x), 77.83, 71.97, 71.65, 68.68, 17.45.
(recrystallized from hexanes and EtOAc); HRMS (ESI,
1
M++1) calcd for C19H21O3S 329.1212, found 329.1215; H
NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.4 Hz, 2H), 7.32
(d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 7.10 (d, J =
8.4 Hz, 2H), 5.23 (d, J = 8.4 Hz, 1H), 3.80 (br s, 1H), 3.51-
3.46 (m, 1H), 2.50 (ddd, J = 2.8, 5.2, 18.0 Hz, 1H), 2.44 (s,
3H), 2.31 (s, 3H), 2.27 (ddd, J = 2.8, 5.2, 18.0 Hz, 1H),
1.84 (t, J = 2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
145.11, 138.30, 136.35, 135.45, 129.64 (2x), 129.18 (2x),
4.2.9.
2-Benzenesulfonyl-1-biphenyl-4-yl-pent-4-yn-1-ol
(5i). Yield = 90% (169 mg); Colorless solid; mp = 140-141
oC (recrystallized from hexanes and EtOAc); HRMS (ESI,