10.1002/ejoc.202100837
European Journal of Organic Chemistry
FULL PAPER
125.3, 123.2, 77.0, 55.0, 35.2, 28.5. HR MS (APCI) m/z: [(M-H2O)+H]+
Calcd for C8H9BrOS 214.9525; Found 214.9526.
Chloroketone 1b (385 mg, 2 mmol) and octylmagnesium chloride (1.3 mL,
2.4 mmol) was stirred for 2 h according to GP1. Column chromatography
(Hexane/AcOEt 9:1, Rf = 0.53) gave 430 mg (70%) of the title compound
as a white solid, Mp 60.3−61.5 °C. 1H NMR (400 MHz, CDCl3) 7.30−7.18
(m, 4H), 4.66 (dd, J = 7.9, 0.9 Hz, 1H), 4.07 (t, J = 7.2 Hz, 1H), 3.29 (d, J
= 15.6 Hz, 1H), 3.06−2.95 (m, 2H), 1.73 (s, 1H), 1.66−1.61 (m, 2H),
1.41−1.24 (m, 12H), 0.89 (t, J = 7.0 Hz, 3H). 13C{1H} NMR (101 MHz,
CDCl3) δ 146.4, 140.7, 127.8, 127.7, 126.1, 124.9, 78.6, 63.6, 48.9, 45.1,
41.6, 33.2, 32.0, 30.0, 29.7, 29.4, 23.0, 22.8, 14.3. HR MS (APCI) m/z:
[(M-H2O)+H]+ Calcd for C19H27O 289.1718; Found 289.1712.
2-Bromo-1-(3-methoxyphenyl)cyclobutan-1-ol (3k)
2-Bromocyclobutanone
(298
mg,
2
mmol)
and
3-
methoxyphenylmagnesium bromide (2.5 mL, 2.4 mmol) was stirred for 1 h
according to GP1. Column chromatography (Hexane/AcOEt 9:1, Rf = 0.30)
gave 375 mg (73%) of the title compound as a colorless oil. 1H NMR (400
MHz, CDCl3) 7.31−7.27 (m, 1H), 7.01−6.97 (m, 2H), 6.86−6.83 (m, 1H),
4.83−4.79 (m, 1H), 3.82 (s, 3H), 2.67−2.52 (m, 4H), 2.42−2.37 (m, 1H).
13C{1H} NMR (101 MHz, CDCl3) δ 159.9, 145.4, 129.8, 125.0, 117.1, 113.4,
110.8, 79.0, 55.4, 53.3, 33.0, 29.1. IR (ATR): 3459 (s), 2942 (w), 1591
(m), 1492 (m), 1462 (m), 1425 (m), 1368 (m), 1328 (m), 1296 (m), 1236
(m), 1209 (w), 1190 (m), 1166 (m), 1125 (m), 1093 (w), 1073 (w), 1045 (w),
1018 (m) cm-1. HR MS (APCI) m/z: [(M-H2O)+H]+ Calcd for C11H13BrO2
239.0066; Found 239.0067.
2-Chloro-1-vinyl-2,2a,7,7a-tetrahydro-1H-cyclobuta[a]inden-1-ol (6e)
Chloroketone 1b (385 mg, 2 mmol) and vinylmagnesium bromide (2.7 mL,
2.4 mmol) was stirred for 2 h according to GP1. Column chromatography
(Hexane/AcOEt 9:1, Rf = 0.44) gave 366 mg (83 %) of the title compound
as a white solid, Mp 74.2−75.7 °C. 1H NMR (400 MHz, CDCl3) 7.31−7.19
(m, 4H), 5.98 (dd, J = 17.1, 10.6 Hz, 1H), 5.36 (dd, J = 17.1, 1.2 Hz, 1H),
5.16 (dd, J = 10.6, 1.2 Hz, 1H), 4.83 (dd, J = 7.9, 1.0 Hz, 1H), 4.12 (t, J =
7.3 Hz, 1H), 3.32 (d, J = 15.6 Hz, 1H), 3.19−3.15 (m, 1H), 3.04 (dd, J =
16.6, 8.2 Hz, 1H), 1.85 (s, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ 146.5,
141.0, 140.4, 127.9, 127.6, 126.2, 124.8, 114.1, 77.9, 63.3, 49.2, 44.8,
32.8. HR MS (APCI) m/z: [(M-H2O)+H]+ Calcd for C13H13ClO 203.0622;
Found 203.0623.
2-Chloro-1-phenyl-2,2a,7,7a-tetrahydro-1H-cyclobuta[a]inden-1-ol
(6a)
Chloroketone 1b (578 mg, 3 mmol) and phenylmagnesium bromide (1.8
mL, 3.6 mmol) was stirred for
2 h according to GP1. Column
chromatography (Hexane/AcOEt 9:1, Rf = 0.43) gave 731 mg (90%) of the
title compound as a white solid, Mp 82.9−83.5 °C. 1H NMR (400 MHz,
CDCl3) 7.51−7.48 (m, 2H), 7.43−7.38 (m, 2H), 7.36−7.23 (m, 5H), 5.15
(dd, J = 8.1, 0.9 Hz, 1H), 4.23 (t, J = 7.5 Hz, 1H), 3.52−3.47 (m, 2H), 3.14
(dd, J = 16.7, 8.3 Hz, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ 146.7, 144.7,
140.4, 128.7, 128.0, 127.9, 127.7, 126.3, 125.0, 124.9, 79.2, 64.5, 49.3,
46.1, 33.3. HR MS (APCI) m/z: [(M-H2O)+H]+ Calcd for C17H15ClO
253.07785; Found 253.07793.
2-Chloro-1-(naphthalen-1-yl)-2,2a,7,7a-tetrahydro-1H-
cyclobuta[a]inden-1-ol (6f)
Chloroketone 1b (385 mg, 2 mmol) and 1-naphthylmagnesium bromide
(4.6 mL, 2.4 mmol) was stirred for 2 h according to GP1. Column
chromatography (Hexane/AcOEt 9:1, Rf = 0.37) gave 359 mg (56%) of the
1
title compound as a white solid, Mp 149.5−151.4 °C. H NMR (400 MHz,
CDCl3) 8.31−8.29 (m, 1H), 7.91−7.82 (m, 2H), 7.62−7.28 (m, 8H), 5.61
(d, J = 8.1 Hz, 1H), 4.24 (t, J = 7.9 Hz, 1H), 4.02 (d, J = 16.6 Hz, 1H), 3.68
(ddt, J = 8.5, 7.2, 1.2 Hz, 1H), 3.44 (dd, J = 16.5, 8.6 Hz, 1H), 2.32 (s, 1H).
13C{1H} NMR (101 MHz, CDCl3) δ 146.1, 140.7, 140.6, 134.7, 130.7, 129.3,
129.2, 128.0, 127.6, 126.34, 126.29, 125.9, 125.8, 125.1, 124.7, 124.0,
80.4, 63.0, 48.9, 46.3, 34.8. IR (ATR): 3521 (s), 3019 (w), 2962 (w),
2909 (w), 1508 (m), 1481 (m), 1459 (w), 1345 (w), 1308 (w), 1282 (w),
1242 (w), 1222 (w), 1179 (w), 1138 (w), 1115 (m), 1065 (w), 1022 (w) cm-
1. HR MS (APCI) m/z: [(M-H2O)+H]+ Calcd for C21H17ClO 303.0935; Found
303.0932.
2-Chloro-1-(4-chlorophenyl)-2,2a,7,7a-tetrahydro-1H-
cyclobuta[a]inden-1-ol (6b)
Chloroketone 1b (385 mg, 2 mmol) and 4-chlorophenylmagnesium
chloride (2.5 mL, 2.4 mmol) was stirred for 2 h according to GP1. Column
chromatography (Hexane/AcOEt 9:1, Rf = 0.42) gave 568 mg (93%) of the
1
title compound as a white solid, Mp 109.1−110.3 °C. H NMR (400 MHz,
CDCl3) 7.45−7.42 (m, 2H), 7.38−7.23 (m, 6H), 5.08 (dd, J = 8.1, 1.0 Hz,
1H), 4.23 (t, J = 7.5 Hz, 1H), 3.48−3.43 (m, 2H), 3.13 (dd, J = 16.7, 8.3 Hz,
1H). 13C{1H} NMR (101 MHz, CDCl3) δ 146.5, 143.1, 140.2, 133.8, 128.8,
128.2, 127.7, 126.6, 126.4, 124.9, 78.8, 64.6, 49.2, 46.2, 33.2. IR (ATR):
3511 (s), 3071 (w), 3056 (w), 2983 (w), 2964 (w), 2930 (w), 2891 (w),
2821 (w), 1489 (m), 1478 (m), 1456 (m), 1418 (m), 1396 (m), 1316 (m),
1291 (m), 1254 (w), 1214 (w), 1174 (w), 1137 (w), 1119 (w), 1091 (m),
1013 (m) cm-1. HR MS (APCI) m/z: [M+H]+ Calcd for C17H14Cl2O 287.0389;
Found 287.0387.
2-Chloro-1-(3-methoxyphenyl)-2,2a,7,7a-tetrahydro-1H-
cyclobuta[a]inden-1-ol (6g)
Chloroketone 1b (385 mg, 2 mmol) and 3-methoxyphenylmagnesium
bromide (2.5 mL, 2.4 mmol) was stirred for 2 h according to GP1. Column
chromatography (Hexane/AcOEt 9:1, Rf = 0.33) gave 565 mg (94%) of the
1
title compound as a white solid, Mp 111.3−113.2 °C. H NMR (400 MHz,
1-([1,1'-Biphenyl]-4-yl)-2-chloro-2,2a,7,7a-tetrahydro-1H-
cyclobuta[a]inden-1-ol (6c)
CDCl3) 7.36−7.23 (m, 5H), 7.10−7.05 (m, 2H), 6.88−6.84 (m, 1H), 5.14
(dd, J = 8.1, 1.1 Hz, 1H), 4.23 (t, J = 7.5 Hz, 1H), 3.84 (s, 3H), 3.51−3.46
(m, 2H), 3.13 (dd, J = 16.7, 8.3 Hz, 1H), 2.18−2.17 (m, 1H). 13C{1H} NMR
(101 MHz, CDCl3) δ 159.9, 146.6, 146.4, 140.4, 129.8, 128.0, 127.7, 126.2,
124.9, 117.3, 113.1, 111.0, 79.1, 64.6, 55.4, 49.2, 46.2, 33.3. IR (ATR):
3532 (s), 3016 (w), 2978 (w), 2946 (w), 2925 (w), 2848 (w), 1610 (s), 1582
(s), 1477 (s), 1443 (s), 1331 (m), 1278 (s), 1245 (s), 1214 (m), 1161 (m),
1135 (m), 1111 (s), 1046 (m), 1024 (m) cm-1. HR MS (APCI) m/z: [(M-
H2O)+H]+ Calcd for C18H17ClO2 283.08842; Found 283.08840.
Chloroketone 1b (385 mg, 2 mmol) and 4-biphenylmagnesium bromide
(5.5 mL, 2.4 mmol) was stirred for 2 h according to GP1. Column
chromatography (Hexane/AcOEt 9:1, Rf = 0.39) gave 513 mg (74%) of the
1
title compound as a white solid, Mp 135.9−136.2 °C. H NMR (400 MHz,
CDCl3) 7.65−7.55 (m, 6H), 7.48−7.42 (m, 2H), 7.38−7.24 (m, 5H),
5.20−5.16 (m, 1H), 4.29−4.23 (m, 1H), 3.56−3.48 (m, 2H), 3.20−3.11 (m,
1H), 2.22−2.20 (m, 1H). 13C{1H} NMR (101 MHz, CDCl3) δ 146.6, 143.6,
140.9, 140.8, 140.4, 129.0, 128.1, 127.7, 127.6, 127.5, 127.3, 126.3, 125.5,
124.9, 79.1, 64.6, 49.3, 46.2, 33.3. IR (ATR): 3521 (m), 3450 (m), 3068
(m), 3033 (m), 2927 (m), 2909 (m), 1487 (m), 1477 (m), 1456 (m), 1369
(m), 1310 (m), 1282 (m), 1264 (m), 1235 (m), 1217 (m),1193 (m), 1136
(m), 1164 (m), 1113 (m), 1084 (w), 1024 (w), 1007 (w) cm-1. HR MS (APCI)
m/z: [(M-H2O)+H]+ Calcd for C23H19ClO 329.1092; Found 329.1087.
1-Allyl-2-chloro-2,2a,7,7a-tetrahydro-1H-cyclobuta[a]inden-1-ol (6h)
Chloroketone 1b (385 mg, 2 mmol) and allylmagnesium chloride (1.7 mL,
2.4 mmol) was stirred for 2 h according to GP1. Column chromatography
(Hexane/AcOEt 9:1, Rf = 0.45) gave 399 mg (85 %) of the title compound
as a white solid, Mp 51.6−52.8 °C. 1H NMR (400 MHz, CDCl3) 7.30−7.19
(m, 4H), 5.91−5.81 (m, 1H), 5.21−5.19 (m, 1H), 5.17−5.15 (m, 1H), 4.71
2-Chloro-1-octyl-2,2a,7,7a-tetrahydro-1H-cyclobuta[a]inden-1-ol (6d)
7
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