10.1002/adsc.202001021
Advanced Synthesis & Catalysis
NMR (400 MHz, CDCl3): δ 7.74 (dd, J = 2.0, 8.0 Hz, 1H),
7.71 (d, J = 8.8 Hz, 2H), 7.40 (d, J = 8.8 Hz, 2H), 7.35 (dt,
J = 1.6, 8.4 Hz, 1H), 6.91 (dt, J = 0.8, 8.0 Hz, 1H), 6.73
(dd, J = 0.4, 8.4 Hz, 1H), 6.67 (d, J = 8.8 Hz, 1H), 6.66 (s,
1H), 6.55 (d, J = 8.8 Hz, 1H), 6.08-5.99 (m, 1H), 5.12 (dq,
J = 1.6, 10.0 Hz, 1H), 5.03 (dq, J = 1.6, 17.2 Hz, 1H), 4.33
(d, J = 0.8 Hz, 1H), 3.78 (s, 3H), 3.75 (s, 3H), 3.74-3.66
(m, 1H), 3.62-3.55 (m, 1H), 1.27 (s, 9H); 13C{1H} NMR
(100 MHz, CDCl3): δ 182.6, 159.1, 158.4, 153.1, 147.9,
137.3, 136.3, 133.8, 132.0, 129.3 (2x), 127.4, 126.7, 125.8
(2x), 121.7, 121.3, 120.3, 118.1, 115.9, 109.8, 73.8, 72.7,
60.8, 55.5, 35.2, 30.9 (3x), 29.9.
6.78 (dt, J = 0.8, 8.4 Hz, 1H), 6.72 (s, 1H), 6.62 (d, J = 8.8
Hz, 1H), 6.52 (d, J = 8.8 Hz, 1H), 6.05-5.95 (m, 1H), 5.11
(dq, J = 1.6, 10.0 Hz, 1H), 5.07 (dq, J = 1.6, 16.8 Hz, 1H),
4.54-4.48 (m, 1H), 4.29 (d, J = 0.8 Hz, 1H), 3.77-3.70 (m,
1H), 3.70 (s, 3H), 3.65-3.60 (m, 1H), 2.36 (s, 3H), 1.25 (d,
J = 6.0 Hz, 3H), 1.23 (d, J = 6.4 Hz, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 182.7, 159.3, 153.1, 145.6, 145.5,
137.2, 136.0, 134.1, 132.3, 129.4 (2x), 129.3 (2x), 127.6,
126.6, 121.3, 121.1, 120.3, 118.1, 115.8, 109.6, 74.6, 73.5,
72.7, 55.3, 30.3, 22.6, 22.5, 21.5.
2-(2-Allyl-3-n-butoxy-4-methoxyphenyl)-3-(toluene-
4-sulfonyl)chroman-4-one (4n). Yield = 82% (427 mg);
Colorless gum; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
2-(2-Allyl-3,4-dimethoxyphenyl)-6-fluoro-3-(toluene-
4-sulfonyl)chroman-4-one (4k). Yield = 76% (377 mg);
Colorless solid; mp = 126-128 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
C30H33O6S 521.1998, found 521.1993; H NMR (400 MHz,
CDCl3): δ 7.75 (dd, J = 1.6, 7.6 Hz, 1H), 7.67 (d, J = 8.0
Hz, 2H), 7.42 (dt, J = 1.6, 8.4 Hz, 1H), 7.23 (d, J = 8.4 Hz,
2H), 6.93 (dt, J = 0.8, 7.6 Hz, 1H), 6.80 (dt, J = 0.8, 8.4 Hz,
1H), 6.69 (s, 1H), 6.65 (d, J = 8.8 Hz, 1H), 6.54 (d, J = 8.8
Hz, 1H), 6.08-5.99 (m, 1H), 5.11 (dq, J = 1.6, 10.0 Hz, 1H),
5.04 (dq, J = 1.6, 16.8 Hz, 1H), 4.31 (d, J = 0.8 Hz, 1H),
3.92 (t, J = 6.4 Hz, 2H), 3.73-3.62 (m, 1H), 3.72 (s, 3H),
3.61-3.57 (m, 1H), 2.37 (s, 3H), 1.77-1.70 (m, 2H), 1.53-
1
calcd for C27H26FO6S 497.1434, found 497.1428; H NMR
(400 MHz, CDCl3): δ 7.68 (d, J = 8.4 Hz, 2H), 7.42 (dd, J
= 3.2, 8.0 Hz, 1H), 7.27 (d, J = 8.0 Hz, 2H), 7.16 (dt, J =
3.2, 7.6 Hz, 1H), 6.81 (dd, J = 4.0, 9.2 Hz, 1H), 6.69 (s,
1H), 6.62 (d, J = 8.8 Hz, 1H), 6.57 (d, J = 8.8 Hz, 1H),
6.09-5.99 (m, 1H), 5.11 (dq, J = 1.6, 10.0 Hz, 1H), 5.01
(dq, J = 1.6, 16.8 Hz, 1H), 4.31 (d, J = 0.8 Hz, 1H), 3.79 (s, 1.44 (m, 2H), 0.96 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (100
3H), 3.76 (s, 3H), 3.72-3.58 (m, 2H), 2.40 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 182.3, 157.1 (d, J = 241.1 Hz),
155.4, 153.3, 148.0, 145.8, 136.3, 134.1, 132.3, 129.6 (2x),
129.3 (2x), 127.1, 125.0 (d, J = 24.3 Hz), 121.8, 120.5 (d, J
= 6.8 Hz), 120.1 (d, J = 6.8 Hz), 115.8, 111.5 (d, J = 23.5
Hz), 109.8, 73.6, 72.0, 60.8, 55.5, 30.0, 21.6. Single-crystal
X-ray diagram: crystal of compound 4k was grown by
slow diffusion of EtOAc into a solution of compound 4k in
CH2Cl2 to yield colorless prisms. The compound
crystallizes in the monoclinic crystal system, space group P
21/c, a = 16.703(5) Å, b = 16.441(5) Å, c = 8.656(3) Å, V
= 2329.9(12) Å3, Z = 4, dcalcd = 1.416 g/cm3, F(000) = 1040,
2θ range 1.755~26.599o, R indices (all data) R1 = 0.1068,
wR2 = 0.2328.
MHz, CDCl3): δ 182.6, 159.3, 153.2, 147.2, 145.5, 137.2,
136.3, 134.1, 132.0, 129.4 (2x), 129.2 (2x), 127.4, 126.6,
121.5, 121.3, 120.2, 118.1, 115.7, 109.7, 73.4, 72.8, 72.6,
55.4, 32.2, 29.9, 21.5, 19.0, 13.8.
2-(2-Allyl-3-methoxyphenyl)-3-(toluene-4-
sulfonyl)chroman-4-one (4o). Yield = 80% (359 mg);
Colorless solid; mp = 164-166 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C26H25O5S 449.1423, found 449.1430; H NMR
(400 MHz, CDCl3): δ 7.75 (dd, J = 1.6, 8.0 Hz, 1H), 7.67
(d, J = 8.0 Hz, 2H), 7.46 (dt, J = 1.6, 8.8 Hz, 1H), 7.24 (d,
J = 8.4 Hz, 2H), 6.99 (t, J = 8.0 Hz, 1H), 6.96 (dt, J = 1.2,
8.4 Hz, 1H), 6.86 (d, J = 0.8, 8.4 Hz, 1H), 6.81 (d, J = 8.0
Hz, 1H), 6.79 (s, 1H), 6.56 (d, J = 8.0 Hz, 1H), 6.07-5.97
(m, 1H), 5.10-5.02 (m, 2H), 4.32 (s, 1H), 3.79 (s, 3H),
3.69-3.54 (m, 2H), 2.38 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 182.3, 159.7, 158.1, 145.6, 137.4, 135.8, 134.1,
129.5 (3x), 129.3 (2x), 127.4, 126.7, 125.9, 121.4, 120.3,
118.0, 117.9, 115.5, 111.2, 73.7, 72.6, 55.7, 29.5, 21.6.
2-(2-Allyl-3,4-dimethoxyphenyl)-7-methoxy-3-
(toluene-4-sulfonyl)chroman-4-one (4l). Yield = 78%
(396 mg); Colorless solid; mp = 173-175 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
1
H]+ calcd for C28H29O7S 509.1634, found 509.1639; H
NMR (400 MHz, CDCl3): δ 7.71 (d, J = 8.8 Hz, 1H), 7.68
(d, J = 8.0 Hz, 2H), 7.26 (d, J = 8.4 Hz, 2H), 6.70 (d, J =
8.4 Hz, 1H), 6.66 (s, 1H), 6.58 (d, J = 8.8 Hz, 1H), 6.52
(dd, J = 2.4, 9.2 Hz, 1H), 6.27 (d, J = 2.4 Hz, 1H), 6.09-
6.00 (m, 1H), 5.11 (dq, J = 1.6, 10.0 Hz, 1H), 5.02 (dq, J =
1.6, 17.2 Hz, 1H), 4.23 (d, J = 0.4 Hz, 1H), 3.79 (s, 6H),
3.76 (s, 3H), 3.75-3.56 (m, 2H), 2.40 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 180.8, 167.3, 161.6, 153.1,
147.8, 145.5, 136.4, 134.3, 132.0, 129.9, 129.5 (2x), 129.3
(2x), 128.6, 127.7, 121.8, 115.8, 114.4, 110.6, 109.9, 73.6,
72.3, 60.8, 55.7, 55.5, 29.9, 21.6.
2-(2-Allyl-3,5-dimethoxyphenyl)-3-(toluene-4-
sulfonyl)chroman-4-one (4p). Two isomers, ratio: 8:1;
Yield = 74% (354 mg); Colorless solid; mp = 175-177 C
o
(recrystallized from hexanes and EtOAc); HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C27H27O6S 479.1528, found
479.1532; for major product: 1H NMR (400 MHz, CDCl3):
δ 7.75 (dd, J = 1.6, 7.6 Hz, 1H), 7.66 (d, J = 8.4 Hz, 2H),
7.47 (dt, J = 1.6, 8.4 Hz, 1H), 7.24 (d, J = 8.4 Hz, 2H),
6.97 (dt, J = 0.8, 7.6 Hz, 1H), 6.89 (dt, J = 0.8, 8.4 Hz, 1H),
6.77 (s, 1H), 6.36 (d, J = 2.4 Hz, 1H), 6.10 (d, J = 2.4 Hz,
1H), 6.04-5.94 (m, 1H), 5.07-4.98 (m, 2H), 4.30 (d, J = 0.8
Hz, 1H), 3.76 (s, 3H), 3.58-3.43 (m, 2H), 3.47 (s, 3H), 2.38
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 182.2, 159.8,
159.1, 158.9, 145.6, 137.4, 136.4, 136.3, 134.1, 129.5 (2x),
129.4, 129.3 (2x), 126.7, 121.5, 117.9, 117.7, 115.1, 102.6,
98.5, 73.8, 72.6, 55.7, 54.9, 29.0, 21.6.
2-(2-Allyl-3-isopropoxy-4-methoxy-phenyl)-3-
(toluene-4-sulfonyl)chroman-4-one (4m). Yield = 83%
o
(420 mg); Colorless solid; mp = 85-87 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
1
H]+ calcd for C29H31O6S 507.1841, found 507.1846; H
NMR (400 MHz, CDCl3): δ 7.75 (dd, J = 2.0, 8.0 Hz, 1H),
7.67 (d, J = 8.0 Hz, 2H), 7.41 (dt, J = 2.0, 8.8 Hz, 1H),
7.22 (d, J = 8.4 Hz, 2H), 6.92 (dt, J = 1.2, 8.0 Hz, 1H),
2-(2-Allyl-3-n-butoxy-5-methoxyphenyl)-3-(toluene-
4-sulfonyl)chroman-4-one (4q). Two isomers, ratio: 6:1;
Yield = 76% (395 mg); Colorless solid; mp = 90-92 C
o
8
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