The Journal of Organic Chemistry
Article
d6) δ 7.34 (dd, J = 26.3, 4.3 Hz, 5H), 7.03−6.94 (m, 2H), 6.49−
6.40 (m, 2H), 5.21 (s, 2H), 3.42−3.30 (m, 2H), 2.76−2.57 (m, 2H),
2.48−2.32 (m, 2H); 13C{1H} NMR (100 MHz, DMSO-d6) δ 176.5,
148.9, 143.3, 133.9, 128.8, 128.1, 125.3, 119.8, 114.8, 88.4, 48.7,
33.2, 28.8; HRMS (ESI) m/z: calcd for C17H18NO2S [M + H]+
300.1058; found 300.1060.
128.7, 128.5, 128.1, 127.2, 124.8, 89.2, 42.7, 37.5, 32.9, 29.0; HRMS
(ESI) m/z: calcd for C18H19O2S [M + H]+ 299.1106; found
299.1104.
5-((Phenylthio)methyl)-5-(p-tolyl)dihydrofuran-2(3H)-one (3ba):
1
pale yellow oil; 80 mg, yield: 89%; H NMR (400 MHz, CDCl3)
δ 7.36−7.29 (m, 2H), 7.29−7.22 (m, 4H), 7.21−7.14 (m, 3H),
3.50−3.38 (m, 2H), 2.77−2.63 (m, 2H), 2.55−2.42 (m, 2H), 2.34
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 175.9, 139.3, 138.0,
136.1, 130.1, 129.3, 129.0, 126.7, 124.7, 88.3, 47.1, 32.6, 29.0, 21.0;
HRMS (ESI) m/z: calcd for C18H19O2S [M + H]+ 299.1106; found
299.1104.
5-(4-Methoxyphenyl)-5-((phenylthio)methyl)dihydrofuran-2(3H)-one
(3ca): colorless oil; 87 mg, yield: 92%; 1H NMR (400 MHz,
CDCl3) δ 7.28−7.18 (m, 5H), 7.18−7.08 (m, 2H), 6.86−6.76 (m,
2H), 3.73 (s, 3H), 3.36 (q, J = 14.0 Hz, 2H), 2.72−2.52 (m, 2H),
2.52−2.33 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 175.9,
159.4, 136.1, 134.2, 130.1, 129.1, 126.7, 126.2, 114.0, 88.2, 55.4,
47.2, 32.6, 29.1; HRMS (ESI) m/z: calcd for C18H19O3S [M + H]+
315.1055; found 315.1054.
5-(((4-Nitrophenyl)thio)methyl)-5-phenyldihydrofuran-2(3H)-one
1
(3ai): yellow oil; 49 mg, yield: 50%; H NMR (400 MHz, CDCl3) δ
8.12−8.04 (m, 2H), 7.44−7.37 (m, 4H), 7.37−7.31 (m, 3H), 3.66−
3.47 (m, 2H), 2.79−2.65 (m, 2H), 2.63−2.46 (m, 2H); 13C{1H}
NMR (100 MHz, CDCl3) δ 175.3, 145.8, 145.7, 141.6, 128.9, 128.6,
127.6, 124.8, 124.0, 87.6, 45.0, 33.2, 28.7; HRMS (ESI) m/z: calcd
for C17H16NO4S [M + H]+ 330.0800; found 330.0800.
5-(((3-Fluorophenyl)thio)methyl)-5-phenyldihydrofuran-2(3H)-one
(3aj): colorless oil; 63 mg; yield: 70%; 1H NMR (400 MHz,
CDCl3) δ 7.45−7.27 (m, 5H), 7.21 (td, J = 8.0, 6.0 Hz, 1H), 7.08
(ddd, J = 7.8, 1.8, 0.9 Hz, 1H), 6.98 (ddd, J = 9.3, 2.5, 1.7 Hz, 1H),
6.87 (tdd, J = 8.4, 2.5, 1.0 Hz, 1H), 3.53−3.40 (m, 2H), 2.78−2.63
(m, 2H), 2.59−2.44 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
175.7, 163.9, 161.5, 142.0, 138.3, 138.2, 130.4, 130.3, 128.8, 128.4,
125.2, 125.2, 124.8, 116.6, 116.3, 113.8, 113.6, 88.0, 46.7, 32.8, 28.9;
HRMS (ESI) m/z: calcd for C17H16FO2S [M + H]+ 303.0855;
found 303.0855.
5-([1,1’-Biphenyl]-4-yl)-5-((phenylthio)methyl)dihydrofuran-2(3H)-
1
one (3da): colorless oil; 88 mg, yield: 81%; H NMR (400 MHz,
CDCl3) δ 7.61−7.53 (m, 4H), 7.44 (t, J = 7.9 Hz, 4H), 7.40−7.29
(m, 3H), 7.26−7.15 (m, 3H), 3.57−3.42 (m, 2H), 2.80−2.66 (m,
2H), 2.62−2.48 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
175.9, 141.2, 141.1, 140.3, 135.9, 130.2, 129.1, 128.9, 127.6, 127.3,
127.1, 126.8, 125.3, 88.2, 47.1, 32.7, 29.0; HRMS (ESI) m/z: calcd
for C23H21O2S [M + H]+ 361.1262; found 361.1261.
5-(4-Fluorophenyl)-5-((phenylthio)methyl)dihydrofuran-2(3H)-one
(3ea): pale yellow oil; 74 mg, yield: 82%; 1H NMR (400 MHz,
CDCl3) δ 7.41−7.33 (m, 2H), 7.33−7.18 (m, 5H), 7.09−6.98 (m,
2H), 3.49−3.37 (m, 2H), 2.81−2.65 (m, 2H), 2.57−2.41 (m, 2H);
13C{1H} NMR (100 MHz, CDCl3) δ 175.6, 163.7, 161.2, 138.0,
138.0, 135.7, 130.3, 129.1, 126.9, 126.8, 126.8, 115.6, 115.4, 87.9,
47.2, 32.7, 28.9; HRMS (ESI) m/z: calcd for C17H16FO2S [M + H]+
303.0855; found 303.0856.
5-(((2-Fluorophenyl)thio)methyl)-5-phenyldihydrofuran-2(3H)-one
1
(3ak): white solid; 81 mg, yield: 89%; mp: 70−71 °C; H NMR
(400 MHz, CDCl3) δ 7.41−7.26 (m, 6H), 7.26−7.19 (m, 1H),
7.08−6.98 (m, 2H), 3.53−3.35 (m, 2H), 2.87−2.67 (m, 2H), 2.58−
2.43 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 175.8, 163.0,
160.6, 142.1, 133.5, 129.5, 129.4, 128.7, 128.3, 124.8, 124.7, 124.6,
122.4, 116.0, 115.8, 88.3, 46.3, 32.6, 28.9; HRMS (ESI) m/z: calcd
for C17H16FO2S [M + H]+ 303.0855; found 303.0854.
5-Phenyl-5-((o-tolylthio)methyl)dihydrofuran-2(3H)-one (3as): col-
1
orless oil; 63 mg; yield 70%; H NMR (400 MHz, CDCl3) δ 7.45−
7.35 (m, 4H), 7.35−7.26 (m, 2H), 7.18−7.08 (m, 3H), 3.42 (q, J =
13.8 Hz, 2H), 2.82−2.67 (m, 2H), 2.56−2.47 (m, 2H), 2.36 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 175.9, 142.4, 138.6,
135.1, 130.4, 129.9, 128.7, 128.2, 126.8, 126.6, 124.8, 88.2, 46.5,
32.7, 29.0, 20.7; HRMS (ESI) m/z: calcd for C18H19O2S [M + H]+
299.1106; found: 299.1108.
5-(4-Chlorophenyl)-5-((phenylthio)methyl)dihydrofuran-2(3H)-one
1
(3fa): yellow oil; 81 mg, yield: 85%; H NMR (400 MHz, CDCl3) δ
7.32 (s, 4H), 7.31−7.27 (m, 2H), 7.26−7.17 (m, 3H), 3.49−3.35
(m, 2H), 2.79−2.66 (m, 2H), 2.55−2.41 (m, 2H); 13C{1H} NMR
(100 MHz, CDCl3) δ 175.5, 140.7, 135.7, 134.2, 130.3, 129.1, 128.8,
127.0, 126.4, 87.8, 47.1, 32.7, 28.9; HRMS (ESI) m/z: calcd for
C17H16ClO2S [M + H]+ 319.0560; found 319.0561.
5-(((3-Hydroxyphenyl)thio)methyl)-5-phenyldihydrofuran-2(3H)-one
(3al): colorless oil; 71 mg, yield: 79%; 1H NMR (400 MHz, DMSO-
d6) δ 9.50 (s, 1H), 7.45−7.36 (m, 4H), 7.36−7.27 (m, 1H), 7.06 (t,
J = 7.9 Hz, 1H), 6.75−6.66 (m, 2H), 6.57 (d, J = 8.0 Hz, 1H), 3.61
(q, J = 13.6 Hz, 2H), 2.80−2.63 (m, 2H), 2.50−2.37 (m, 2H);
13C{1H} NMR (100 MHz, DMSO-d6) δ 176.4, 158.1, 143.0, 137.6,
130.3, 128.9, 128.3, 125.2, 119.3, 115.4, 113.6, 88.0, 44.5, 33.7, 28.7;
HRMS (ESI) m/z: calcd for C17H17O3S [M + H]+ 301.0898; found
301.0899.
5-(4-Bromophenyl)-5-((phenylthio)methyl)dihydrofuran-2(3H)-one
1
(3ga): yellow oil; 82 mg, yield: 84%; H NMR (400 MHz, CDCl3)
δ 7.57−7.43 (m, 2H), 7.35−7.15 (m, 7H), 3.49−3.35 (m, 2H),
2.79−2.66 (m, 2H), 2.54−2.41 (m, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 175.5, 141.3, 135.7, 131.8, 130.4, 129.1, 127.0, 126.7,
122.4, 87.8, 47.1, 32.7, 28.9; HRMS (ESI) m/z: calcd for
C17H16BrO2S [M + H]+ 363.0054; found 363.0051.
5-Phenyl-5-((thiophen-2-ylthio)methyl)dihydrofuran-2(3H)-one
1
(3am): pale yellow oil; 77 mg, yield: 88%; H NMR (400 MHz,
5-(3-Nitrophenyl)-5-((phenylthio)methyl)dihydrofuran-2(3H)-one
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CDCl3) δ 7.38 (d, J = 4.1 Hz, 4H), 7.35−7.29 (m, 2H), 7.04 (dd, J
= 3.5, 1.3 Hz, 1H), 6.92 (dd, J = 5.4, 3.6 Hz, 1H), 3.45−3.31 (m,
2H), 2.79−2.69 (m, 2H), 2.59−2.49 (m, 2H); 13C{1H} NMR (100
MHz, CDCl3) δ 175.9, 142.1, 134.4, 134.0, 129.7, 128.7, 128.3,
127.7, 124.9, 88.2, 51.5, 32.7, 29.0; HRMS (ESI) m/z: calcd for
C15H15O2S2 [M + H]+ 291.0513; found 291.0517.
(3ha): yellow oil; 51 mg, yield: 52%; H NMR (400 MHz, CDCl3)
δ 8.20 (t, J = 2.0 Hz, 1H), 8.13 (ddd, J = 8.1, 2.2, 1.0 Hz, 1H), 7.77
(ddd, J = 7.8, 1.9, 1.1 Hz, 1H), 7.53 (t, J = 8.0 Hz, 1H), 7.31−7.26
(m, 2H), 7.25−7.15 (m, 3H), 3.47 (d, J = 1.0 Hz, 2H), 2.86−2.71
(m, 2H), 2.60−2.47 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
175.0, 148.3, 144.2, 135.1, 131.2, 130.5, 129.8, 129.2, 127.2, 123.2,
120.4, 87.4, 46.9, 32.8, 28.7; HRMS (ESI) m/z: calcd for
C17H16NO4S [M + H]+ 330.0800; found 330.0800.
5-Phenyl-5-((pyridin-2-ylthio)methyl)dihydrofuran-2(3H)-one (3an):
1
colorless oil; 56 mg, yield: 65%; H NMR (400 MHz, CDCl3) δ
8.42 (ddd, J = 5.0, 1.9, 1.0 Hz, 1H), 7.50−7.45 (m, 3H), 7.41−7.29
(m, 3H), 7.18 (dt, J = 8.0, 1.0 Hz, 1H), 7.01 (ddd, J = 7.3, 5.0, 1.1
Hz, 1H), 4.11 (d, J = 14.4 Hz, 1H), 3.72 (d, J = 14.4 Hz, 1H),
2.79−2.68 (m, 2H), 2.53−2.39 (m, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 176.3, 157.4, 149.2, 142.8, 136.2, 128.6, 128.1, 124.9,
122.6, 120.0, 88.5, 40.1, 32.5, 29.1; HRMS (ESI) m/z: calcd for
C16H16NO2S [M + H]+ 286.0902; found 286.0903.
5-Methyl-5-((phenylthio)methyl)dihydrofuran-2(3H)-one (3la): col-
orless oil; 47 mg; yield 70%; H NMR (400 MHz, CDCl3) δ 7.44−
1
7.37 (m, 2H), 7.30 (dd, J = 8.4, 6.7 Hz, 2H), 7.25−7.18 (m, 1H),
3.23 (d, J = 3.2 Hz, 2H), 2.64 (ddd, J = 9.7, 8.5, 7.1 Hz, 2H), 2.29
(ddd, J = 13.1, 9.9, 7.1 Hz, 1H), 2.01 (ddd, J = 13.1, 9.6, 7.1 Hz,
1H), 1.50 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 176.1,
136.0, 130.1, 129.2, 126.9, 86.0, 45.0, 31.9, 29.2, 26.3; HRMS (ESI)
m/z: calcd for C12H15O2S [M + H]+ 223.0793; found: 223.0793.
3-(((4-Methoxyphenyl)thio)methyl)-3-phenylisobenzofuran-1(3H)-
5-((Benzylthio)methyl)-5-phenyldihydrofuran-2(3H)-one (3ao): col-
1
orless oil; 64 mg, yield: 71%; H NMR (400 MHz, CDCl3) δ 7.41−
1
7.34 (m, 4H), 7.34−7.25 (m, 5H), 7.24−7.19 (m, 1H), 3.65 (s, 2H),
2.92−2.80 (m, 2H), 2.76−2.63 (m, 2H), 2.55−2.41 (m, 2H);
13C{1H} NMR (100 MHz, CDCl3) δ 176.1, 142.7, 137.6, 129.2,
one (3ic): colorless oil; 67 mg, yield: 62%; H NMR (400 MHz,
CDCl3) δ 7.99−7.90 (m, 1H), 7.56−7.48 (m, 4H), 7.42−7.28 (m,
4H), 7.13−7.04 (m, 2H), 6.74−6.64 (m, 2H), 3.79 (s, 2H), 3.76 (s,
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J. Org. Chem. 2021, 86, 8620−8629