M.-Y. Chang et al. / Tetrahedron xxx (2015) 1e7
5
1
J¼9.1 Hz, 2ꢁ), 129.17 (2ꢁ), 129.68, 127.04 (2ꢁ), 114.50 (d, J¼21.2 Hz,
calcd for C19
CDCl ):
H), 1.82 (t, J¼6.8 Hz, 2H), 1.29 (s, 6H); C NMR (100 MHz, CDCl
H
21
O
3
S 329.1212, found 329.1214; H NMR (400 MHz,
2
ꢁ), 113.12, 76.68, 32.37, 26.14 (2ꢁ), 21.47, 20.72.
3
d
7.52e7.43 (m, 3H), 7.38e7.21 (m, 7H), 2.57 (t, J¼6.8 Hz,
13
2
d
3
):
4
2
.2.3. 2,2-Dimethyl-5-(toluene-4-sulfonyl)-6-p-tolyl-3,4-dihydro-
161.49, 142.28, 134.63, 132.17, 129.43 (2ꢁ), 129.39, 128.44 (2ꢁ),
H-pyran (5d). Yield¼65% (231 mg); Colorless gum; HRMS (ESI,
127.45 (2ꢁ), 126.98 (2ꢁ), 112.56, 76.88, 32.38, 26.14 (2ꢁ), 20.64.
þ
1
M þ1) calcd for C21
25 3
H O S 357.1524, found 357.1523; H NMR
(
400 MHz, CDCl
3
):
d
7.43 (d, J¼8.4 Hz, 2H), 7.17e7.10 (m, 6H), 2.50 (t,
4.2.9. 5-Benzenesulfonyl-6-(4-fluorophenyl)-2,2-dimethyl-3,4-
dihydro-2H-pyran (5j). Yield¼82% (284 mg); Colorless gum; HRMS
J¼6.8 Hz, 2H), 2.38 (s, 3H), 2.36 (s, 3H), 1.79 (t, J¼6.8 Hz, 2H), 1.27 (s,
13
þ
1
6
H); C NMR (100 MHz, CDCl ): 161.28, 142.89, 139.49, 139.46,
3
d
(ESI, M þ1) calcd for C19
3
H20FO S 347.1117, found 347.1121; H NMR
1
32.05, 129.34 (2ꢁ), 129.08 (2ꢁ), 128.15 (2ꢁ), 127.16 (2ꢁ), 112.24,
3
(400 MHz, CDCl ): d 7.53e7.44 (m, 3H), 7.37e7.33 (m, 2H),
76.68, 32.44, 26.18 (2ꢁ), 21.48, 21.45, 20.72.
7.25e7.20 (m, 2H), 7.00e6.94 (m, 2H), 2.54 (t, J¼6.8 Hz, 2H), 1.80 (t,
13
J¼6.8 Hz, 2H), 1.27 (s, 6H); C NMR (100 MHz, CDCl
3
): d 163.31 (d,
4
.2.4. 2,2-Dimethyl-6-(3-nitrophenyl)-5-(toluene-4-sulfonyl)-3,4-
J¼247.8 Hz), 160.31, 142.10, 132.31, 131.52 (d, J¼8.3 Hz, 2ꢁ), 130.62
(d, J¼3.1 Hz), 128.49 (2ꢁ), 126.84 (2ꢁ), 114.46 (d, J¼22.0 Hz, 2ꢁ),
dihydro-2H-pyran (5e). Yield¼83% (321 mg); Colorless solid;
ꢀ
mp¼148e149 C (recrystallized from hexanes and EtOAc); HRMS
112.87, 77.00, 32.26, 26.04 (2ꢁ), 20.63; Anal. Calcd for C19
3
H19FO S:
þ
1
(
ESI, M þ1) calcd for C20
H22NO
5
S 388.1219, found 388.1222;
H
C, 65.88; H, 5.53. Found: C, 66.07; H, 5.68.
NMR (400 MHz, CDCl
3
):
d
8.23 (ddd, J¼1.2, 2.4, 8.4 Hz, 1H), 7.95 (t,
J¼2.4 Hz, 1H), 7.71 (dt, J¼1.2, 8.4 Hz, 1H), 7.53 (t, J¼8.0 Hz, 1H), 7.43
4.2.10. 5-Benzenesulfonyl-6-biphenyl-4-yl-2,2-dimethyl-3,4-
(
(
d, J¼8.4 Hz, 2H), 7.20 (d, J¼8.0 Hz, 2H), 2.51 (t, J¼6.8 Hz, 2H), 2.37
dihydro-2H-pyran (5k). Yield¼83% (335 mg); Colorless gum; HRMS
13
þ
1
s, 3H), 1.81 (t, J¼6.8 Hz, 2H), 1.30 (s, 6H); C NMR (100 MHz,
):
158.05, 143.72, 138.65, 136.38, 135.95, 129.52, 129.45 (2ꢁ),
28.46, 127.00 (2ꢁ), 124.05, 124.04, 114.13, 77.64, 32.13, 26.09 (2ꢁ),
1.38, 20.44; Anal. Calcd for C20 S: C, 62.00; H, 6.46. Found:
C, 62.21; H, 6.68. Single-crystal X-ray diagram: crystal of compound
e was grown by slow diffusion of EtOAc into a solution of com-
pound 5e in CH Cl to yield colorless prisms. The compound crys-
tallizes in the triclinic crystal system, space group P-1,
(ESI, M þ1) calcd for C25
25 3
H O S 405.1524, found 405.1529; H NMR
CDCl
3
d
3
(400 MHz, CDCl ): d 7.61e7.43 (m, 10H), 7.39e7.28 (m, 4H), 2.61 (t,
1
3
1
J¼6.8 Hz, 2H), 1.84 (t, J¼6.8 Hz, 2H), 1.32 (s, 6H); C NMR (100 MHz,
2
H21NO
5
CDCl ):
3
d
161.13, 142.22, 140.50, 133.46, 132.16, 129.92 (2ꢁ), 129.62,
128.81 (2ꢁ), 128.39 (2ꢁ), 127.52, 127.10 (2ꢁ), 126.99 (2ꢁ), 126.16
(2ꢁ), 112.82, 76.92, 32.35, 26.11 (2ꢁ), 20.63.
5
2
2
4.2.11. 5-Methanesulfonyl-2,2-dimethyl-6-phenyl-3,4-dihydro-2H-
ꢀ
ꢀ
ꢀ
ꢀ
3
ꢀ
a¼9.0782(4) A, b¼9.6023(5) A, c¼11.7138(6) A, V¼915.61(8) A ,
pyran (5l). Yield¼76% (202 mg); Colorless solid; mp¼99e100
C
3
ꢀ
þ
Z¼2, dcalcd¼1.405 mg/cm , F(000)¼408, 2
q
range 1.829e26.468 , R
(recrystallized from hexanes and EtOAc); HRMS (ESI, M þ1) calcd
1
indices (all data) R1¼0.0401, wR2¼0.0839.
for C14
19 3 3
H O S 267.1055, found 267.1057; H NMR (400 MHz, CDCl ):
d
7.44e7.36 (m, 5H), 2.65 (s, 3H), 2.60 (t, J¼6.8 Hz, 2H), 1.86 (t,
13
4
. 2 . 5 . 2 , 2 - D i m e t h y l - 5 - ( t o l u e n e - 4 - s u l f o n y l ) - 6 - ( 4 -
J¼6.8 Hz, 2H), 1.37 (s, 6H); C NMR (100 MHz, CDCl
3
): d 160.75,
trifluoromethylphenyl)-3,4-dihydro-2H-pyran
(5f). Yield¼85%
134.71, 129.82, 129.28 (2ꢁ), 127.93 (2ꢁ), 112.56, 77.32, 43.18, 32.36,
26.17 (2ꢁ), 20.25. Single-crystal X-ray diagram: crystal of com-
pound 5l was grown by slow diffusion of EtOAc into a solution of
þ
(
349 mg); Colorless gum; HRMS (ESI, M þ1) calcd for C21
22 3 3
H F O S
1
3
411.1242, found 411.1245; H NMR (400 MHz, CDCl ): d 7.56 (d,
J¼8.0 Hz, 2H), 7.41 (d, J¼8.4 Hz, 2H), 7.38 (d, J¼8.0 Hz, 2H), 7.16 (d,
compound 5l in CH
2 2
Cl to yield colorless prisms. The compound
J¼8.0 Hz, 2H), 2.52 (t, J¼6.8 Hz, 2H), 2.37 (s, 3H), 1.81 (t, J¼6.8 Hz,
crystallizes in the monoclinic crystal system, space group P 21/c,
H), 1.29 (s, 6H); 13C NMR (100 MHz, CDCl
):
d
159.24, 143.38,
a¼12.3042(8) A, b¼29.754(2) A, c¼11.0845(7) A, V¼4055.4(5) A ,
ꢀ
ꢀ
ꢀ
ꢀ
3
2
3
3
ꢀ
1
38.84, 138.39, 131.29, 130.97, 129.82 (2ꢁ), 129.26 (2ꢁ), 124.43 (d,
J¼3.8 Hz, 2ꢁ), 124.35 (d, J¼3.8 Hz, 2ꢁ), 113.67, 77.26, 32.20, 26.10
2ꢁ), 21.40, 20.45; Anal. Calcd for C21 S: C, 61.45; H, 5.16.
Found: C, 61.78; H, 5.31.
Z¼12, dcalcd¼1.309 mg/cm , F(000)¼1704, 2
q range 1.369e26.386 ,
R indices (all data) R1¼0.0509, wR2¼0.1159.
(
21 3 3
H F O
4.2.12. 5-Hydroxy-2-methanesulfonyl-5-methyl-1-p-tolyl-hexan-1-
one (5me1). Yield¼62% (185 mg); Colorless gum; HRMS (ESI,
þ
1
4
.2.6. 6-Biphenyl-4-yl-2,2-dimethyl-5-(toluene-4-sulfonyl)-3,4-
M þ1) calcd for C15
23 5
H O S 299.1317, found 299.1319; H NMR
dihydro-2H-pyran (5g). Yield¼80% (334 mg); Colorless gum; HRMS
(400 MHz, CDCl
3
):
d
7.93 (d, J¼8.4 Hz, 2H), 7.31 (d, J¼7.6 Hz, 2H),
þ
1
(
(
ESI, M þ1) calcd for C26
27
H O
3
S 419.1681, found 419.1687; H NMR
4.98 (dd, J¼5.6, 8.8 Hz, 1H), 2.94 (s, 3H), 2.42 (s, 3H), 2.38e2.31 (m,
2H), 1.73 (s, 1H), 1.54e1.47 (m, 1H), 1.42e1.35 (m, 1H), 1.21 (s, 3H),
400 MHz, CDCl
3
):
d
7.61e7.59 (m, 2H), 7.54e7.43 (m, 6H),
13
7
.39e7.33 (m, 3H), 7.14 (d, J¼8.0 Hz, 2H), 2.57 (t, J¼6.8 Hz, 2H), 2.37
3
1.19 (s, 3H); C NMR (100 MHz, CDCl ): d 193.45, 145.75, 134.31,
13
(
s, 3H), 1.83 (t, J¼6.8 Hz, 2H), 1.31 (s, 6H); C NMR (100 MHz,
CDCl ):
161.76, 142.96, 142.24, 140.62, 133.68, 129.93 (2ꢁ), 129.70,
29.07 (2ꢁ), 128.75 (2ꢁ), 127.52, 127.16 (2ꢁ), 127.14 (2ꢁ), 126.17
2ꢁ), 112.94, 77.32, 32.40, 26.17 (2ꢁ), 21.46, 20.68.
129.65 (2ꢁ), 129.38 (2ꢁ), 70.38, 68.66, 40.11, 37.24, 29.46, 29.02,
3
d
23.98, 21.72.
1
(
4.2.13. 6-Biphenyl-4-yl-5-methanesulfonyl-2,2-dimethyl-3,4-
dihydro-2H-pyran (5n). Yield¼83% (284 mg); Colorless solid;
ꢀ
4
.2.7. 2,2-Dimethyl-6-naphthalen-2-yl-5-(toluene-4-sulfonyl)-3,4-
mp¼173e174 C (recrystallized from hexanes and EtOAc); HRMS
þ
1
dihydro-2H-pyran (5h). Yield¼72% (282 mg); Colorless gum; HRMS
(ESI, M þ1) calcd for C20
23 3
H O S 343.1368, found 343.1371; H NMR
þ
1
(
(
ESI, M þ1) calcd for C24
H
25
O
3
S 393.1524, found 393.1520; H NMR
3
(400 MHz, CDCl ): d 7.65e7.59 (m, 4H), 7.54e7.51 (m, 2H),
400 MHz, CDCl
3
):
d
7.84e7.76 (m, 2H), 7.74 (d, J¼8.4 Hz,1H), 7.70 (s,
7.47e7.42 (m, 2H), 7.39e7.34 (m, 1H), 2.72 (s, 3H), 2.64 (t, J¼6.8 Hz,
13
1
1
H), 7.53e7.47 (m, 2H), 7.34 (d, J¼8.4 Hz, 2H), 7.29 (dd, J¼1.6, 8.4 Hz,
2H), 1.89 (t, J¼6.8 Hz, 2H), 1.41 (s, 6H); C NMR (100 MHz, CDCl
3
):
H), 7.02 (d, J¼8.0 Hz, 2H), 2.62 (t, J¼6.8 Hz, 2H), 2.31 (s, 3H), 1.86 (t,
d
160.46, 142.59, 140.24, 133.53, 129.72 (2ꢁ), 128.75 (2ꢁ), 127.65,
1
3
J¼6.8 Hz, 2H), 1.33 (s, 6H); C NMR (100 MHz, CDCl
3
):
d
161.03,
127.14 (2ꢁ), 126.58 (2ꢁ), 112.55, 77.03, 43.17, 32.30, 26.16 (2ꢁ),
1
42.94, 139.44, 133.55, 132.28, 132.09, 129.41, 128.99 (2ꢁ), 128.40,
20.30.
127.65, 127.12 (2ꢁ), 127.08, 126.78, 126.45, 126.13, 113.39, 76.92,
3
2.50, 26.20 (2ꢁ), 21.39, 20.73.
4.2.14. 5-(4-Fluorobenzenesulfonyl)-2,2-dimethyl-6-phenyl-3,4-
dihydro-2H-pyran (5o). Yield¼82% (284 mg); Colorless gum; HRMS
þ
1
4.2.8. 5-Benzenesulfonyl-2,2-dimethyl-6-phenyl-3,4-dihydro-2H-py-
(ESI, M þ1) calcd for C19
3
H20FO S 347.1117, found 347.1124; H NMR
þ
ran (5i). Yield¼80% (262 mg); Colorless gum; HRMS (ESI, M þ1)
3
(400 MHz, CDCl ): d 7.49e7.44 (m, 2H), 7.39e7.34 (m, 1H),