10.1002/chem.201604585
Chemistry - A European Journal
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CDCl3): δ: 161.5 (d, J = 245.5 Hz), 142.3 (d, J = 2.3 Hz), 134.8, 132.8 (d,
J = 3.2 Hz), 127.1 (d, J = 7.8 Hz), 115.3 (d, J = 21.4 Hz), 41.9, 33.0, 32.9,
32.3, 27.4, 22.9, 14.3, 14.2. ppm. HRMS (EI): calcd for C16H21F+: 232.1627,
found 232.1624. IR (, cm-1) 2957 (m), 2923 (m), 2855 (m), 1655 (vw),
1601 (w), 1507 (vs), 1467 (w), 1408 (vw), 1376 (w), 1324 (w), 1294 (w),
1230 (s), 1182 (vw), 1155 (m), 1104 (w), 1069 (vw), 1012 (vw).
Using 17d as iodide and (3-nitrophenyl)boronic acid according to general
procedure E provided 20g (69 mg, 70%) as a colorless oil. Rf = 0.67 (95:5
hexane:EtOAc, UV, KMnO4). 1H NMR (400 MHz, CDCl3): δ: 8.11 (t, J = 2.0
Hz, 1H), 8.03 (ddd, J = 8.2, 2.3, 1.0 Hz, 1H), 7.61 (dt, J = 7.7, 1.3 Hz, 1H),
7.48 (t, J = 7.9 Hz, 1H), 7.35 – 7.27 (m, 2H), 7.23 – 7.18 (m, 3H), 2.83 (ddd,
J = 12.1, 4.5, 2.2 Hz, 1H), 2.72 (dt, J = 9.0, 6.7 Hz, 3H), 2.28 (dt, J = 12.1,
2.1 Hz, 1H), 2.11 – 2.03 (m, 1H), 2.02 (d, J = 1.7 Hz, 3H), 1.67 ppm (dtd,
J = 13.4, 9.4, 6.1 Hz, 1H).13C NMR (101 MHz, CDCl3): δ: 148.6, 146.5,
142.5, 137.8, 134.2, 131.4, 129.3, 128.6, 128.5, 125.9, 121.1, 120.2, 41.7,
34.7, 34.0, 32.7, 14.4 ppm. HRMS (EI): calcd for C19H19NO2+: 293.1416,
found 293.1409. IR (, cm-1) 3085 (vw), 3062 (vw), 3026 (w), 2914 (w),
2855 (w), 1700 (w), 1696 (w), 1684 (w), 1653 (w), 1603 (w), 1527 (vs),
1496 (m), 1454 (w), 1438 (w), 1349 (vs), 1181 (w), 1079 (w).
1-Fluoro-4-(2-methyl-3-phenethylcyclobut-1-en-1-yl) benzene (20c):
Using 17d as iodide and (4-fluorophenyl)boronic acid according to general
procedure E provided 20c (71 mg, 80%) as a colorless oil. Rf = 0.51
1
(hexane, UV, KMnO4). H NMR (400 MHz, CDCl3): δ: 7.29 (ddd, J = 7.8,
4.7, 2.0 Hz, 4H), 7.23 – 7.16 (m, 3H), 7.05 – 6.96 (m, 2H), 2.79 – 2.63 (m,
4H), 2.20 (dp, J = 12.1, 2.0 Hz, 1H), 2.08 – 1.97 (m, 1H), 1.93 (q, J = 2.0
Hz, 3H), 1.72 – 1.58 ppm (m, 1H). 13C NMR (101 MHz, CDCl3): δ: 161.6
(d, J = 245.7 Hz), 142.8, 141.8 (d, J = 2.2 Hz), 135.0, 132.6 (d, J = 3.3 Hz),
128.6, 128.4, 127.2 (d, J = 7.8 Hz), 125.8, 115.3 (d, J = 21.4 Hz), 41.4,
35.0, 34.1, 32.8, 14.2 ppm. HRMS (EI): calcd for C19H19F+: 266.1371,
found 266.1461. IR (, cm-1) 3027 (w), 2911 (m), 2851 (w), 2363 (vw), 2338
(vw), 1654 (w), 1601 (w), 1507 (vs), 1455 (w), 1437 (w), 1374 (w), 1323
(w), 1229 (m), 1156 (m), 1105 (vw), 1070 (vw).
1-(2-Methyl-3-phenethylcyclobut-1-en-1-yl)-4-phenoxybenzene (20h):
Using 17d as iodide and (4-phenoxyphenyl)boronic acid according to
general procedure E provided 20h (104 mg, 91%) as a colorless oil. Rf =
0.15 (hexane, UV, KMnO4). 1H NMR (400 MHz, CDCl3): δ: 7.38 – 7.27 (m,
6H), 7.25 – 7.18 (m, 3H), 7.13 – 7.08 (m, 1H), 7.01 (td, J = 7.7, 7.0, 1.6 Hz,
4H), 2.78 (ddq, J = 11.7, 5.1, 2.3 Hz, 1H), 2.70 (ddt, J = 11.0, 9.4, 4.7 Hz,
3H), 2.23 (dp, J = 12.1, 2.2 Hz, 1H), 2.05 (dddd, J = 14.1, 9.6, 6.6, 4.7 Hz,
(2-Methyl-3-phenethylcyclobut-1-en-1-yl)benzene (20d): Using 17d as
iodide and phenylboronic acid according to general procedure E provided
1H), 1.96 (q, J = 2.0 Hz, 3H), 1.67 ppm (dtd, J = 13.3, 9.5, 6.0 Hz, 1H). 13
C
NMR (101 MHz, CDCl3): δ: 157.5, 155.7, 142.9, 141.3, 135.3, 131.9, 129.8,
128.6, 128.4, 127.0, 125.8, 123.2, 119.1, 118.8, 41.4, 35.0, 34.1, 32.7,
14.2. ppm. HRMS (EI): calcd for C25H24O+: 340.1827, found 340.1813. IR
(, cm-1) 3061 (vw), 3027 (w), 2909 (w), 2850 (w), 1654 (vw), 1588 (m),
1503 (s), 1488 (vs), 1454 (m), 1374 (w), 1325 (w), 1231 (vs), 1201 (m),
1164 (m), 1111 (w), 1071 (w), 1023 (w).
1
20d (78 mg, 94%) as a colorless oil. Rf = 0.71 (hexane, UV, KMnO4). H
NMR (400 MHz, CDCl3): δ: 7.36 – 7.27 (m, 6H), 7.24 – 7.16 (m, 4H), 2.79
(ddt, J = 11.7, 4.0, 1.9 Hz, 1H), 2.75 – 2.64 (m, 3H), 2.24 (dp, J = 12.1, 2.2
Hz, 1H), 2.09 – 1.99 (m, 1H), 1.98 – 1.95 (m, 3H), 1.66 ppm (dtd, J = 13.4,
9.5, 6.0 Hz, 1H). 13C NMR (101 MHz, CDCl3): δ: 142.9, 142.6, 136.3, 136.1,
128.6, 128.4, 126.6, 125.8, 125.7, 41.4, 35.0, 34.1, 32.6, 14.3 ppm. (2
aromatic 13C signals overlapping) HRMS (EI): calcd for C19H20+: 248.1565,
found 248.1544. IR (, cm-1) 3061 (w), 3026 (w), 2911 (m), 2851 (w), 2363
(vw), 2338 (vw), 1688 (vw), 1656 (vw), 1651 (vw), 1601 (w), 1494 (m),
1453 (w), 1446 (m), 1374 (w), 1322 (w), 1181 (w), 1056 (w), 1030 (w).
2-(2-Methyl-3-phenethylcyclobut-1-en-1-yl)benzo[b] thiophene (20i):
Using 17d as iodide and benzo[b]thiophen-2-ylboronic acid according to
general procedure E provided 20i (77 mg, 76%) as a colorless oil. Rf =
0.28 (hexane, UV, KMnO4). 1H NMR (400 MHz, CDCl3): δ: 7.77 (d, J = 7.9
Hz, 1H), 7.70 (d, J = 7.4 Hz, 1H), 7.35 – 7.26 (m, 4H), 7.25 – 7.17 (m, 3H),
7.04 (s, 1H), 2.86 (ddt, J = 11.6, 4.2, 2.1 Hz, 1H), 2.80 – 2.65 (m, 3H), 2.32
(dt, J = 11.9, 2.1 Hz, 1H), 2.04 (dddd, J = 13.9, 9.3, 6.7, 4.9 Hz, 1H), 1.97
(q, J = 2.0 Hz, 3H), 1.71 ppm (dtd, J = 13.4, 9.3, 6.3 Hz, 1H).13C NMR (101
MHz, CDCl3): δ: 144.2, 142.7, 139.8, 139.7, 139.0, 131.1, 128.6, 128.5,
125.9, 124.5, 124.1, 123.4, 122.3, 119.2, 42.3, 34.9, 34.0, 33.6, 14.3 ppm.
HRMS (EI): calcd for C21H20S+: 304.1286, found 304.1278. IR (, cm-1)
3060 (w), 3025 (w), 2913 (m), 2851 (w), 1655 (w), 1603 (w), 1496 (m),
1455 (m), 1436 (m), 1372 (w), 1330 (w), 1303 (m), 1250 (w), 1155 (w),
1066 (w), 1030 (w), 1016 (w).
tert-Butyl
carbamate
(3-(2-methyl-3-phenethylcyclobut-1-en-1-yl)phenyl)
(20e): Using 17d as iodide and (3-((tert-
butoxycarbonyl)amino)phenyl)boronic acid according to general
procedure E provided 20e (76 mg, 62%) as a colorless oil. Rf = 0.50 (95:5
hexane:EtOAc, UV, KMnO4). 1H NMR (400 MHz, CDCl3): δ: 7.33 – 7.14
(m, 8H), 7.02 (dt, J = 6.8, 1.7 Hz, 1H), 6.44 (s, 1H), 2.77 (ddd, J = 12.2,
4.5, 2.2 Hz, 1H), 2.73 – 2.61 (m, 3H), 2.22 (dt, J = 12.1, 2.1 Hz, 1H), 2.09
– 1.97 (m, 1H), 2.00 – 1.93 (m, 3H), 1.64 (dtd, J = 13.3, 9.5, 6.0 Hz, 1H),
1.52 ppm (s, 9H). 13C NMR (101 MHz, CDCl3): δ: 156.2, 143.1, 142.9,
138.5, 137.1, 135.9, 129.0, 128.6, 128.4, 125.8, 120.5, 118.3, 116.8, 80.6,
+
41.4, 34.9, 34.1, 32.7, 28.5, 14.3 ppm. HRMS (EI): calcd for C24H29NO2
:
5-(2-Methyl-3-phenethylcyclobut-1-en-1-yl)benzo[d] [1,3] dioxole
(20j): Using 17d as iodide and benzo[d][1,3]dioxol-5-ylboronic acid
according to general procedure E provided 20j (80 mg, 81%) as a colorless
oil. Rf = 0.33 (hexane, UV, KMnO4). 1H NMR (400 MHz, CDCl3): δ: 7.31 –
7.26 (m, 2H), 7.23 – 7.17 (m, 3H), 6.86 – 6.83 (m, 1H), 6.78 (s, 2H), 5.94
(s, 2H), 2.77 – 2.60 (m, 4H), 2.18 (dt, J = 12.1, 2.1 Hz, 1H), 2.08 – 1.96 (m,
363.2198, found 363.2198. IR (, cm-1) 3331 (w), 2978 (w), 2927 (w), 2856
(w), 2363 (vw), 2339 (vw), 1728 (m), 1700 (m), 1654 (w), 1606 (m), 1586
(m), 1539 (m), 1493 (m), 1454 (m), 1439 (m), 1421 (w), 1392 (w), 1367
(m), 1285 (m), 1236 (m), 1158 (vs), 1055 (w), 1029 (w).
3-(2-Methyl-3-phenethylcyclobut-1-en-1-yl)thiophene (20f): Using 17d
as iodide and thiophen-3-ylboronic acid according to general procedure E
provided 20f (90 mg, 98%) as a colorless oil. Rf = 0.38 (hexane, UV,
KMnO4). 1H NMR (400 MHz, CDCl3): δ: 7.29 (td, J = 6.5, 5.6, 3.5 Hz, 3H),
7.24 – 7.16 (m, 4H), 7.09 (d, J = 2.5 Hz, 1H), 2.81 – 2.67 (m, 4H), 2.22 (dp,
J = 11.9, 2.1 Hz, 1H), 2.02 (dddd, J = 13.9, 9.5, 6.6, 4.7 Hz, 1H), 1.90 (q,
J = 2.0 Hz, 3H), 1.67 ppm (dtd, J = 13.3, 9.3, 6.1 Hz, 1H). 13C NMR (101
MHz, CDCl3): δ: 142.9, 140.3, 138.3, 131.9, 128.6, 128.4, 125.8, 125.7,
119.9, 42.0, 35.1, 34.1, 33.3, 14.0 ppm. (2 aromatic 13C signals
overlapping) HRMS (EI): calcd for C17H18S+: 254.1129, found 254.1122. IR
(, cm-1) 3104 (vw), 3084 (vw), 3062 (vw), 3026 (w), 2909 (m), 2850 (w),
1690 (w), 1603 (w), 1496 (m), 1453 (m), 1413 (w), 1371 (w), 1298 (w),
1234 (w), 1202 (w), 1180 (w), 1085 (w), 1076 (w), 1030 (w).
1H), 1.92 (q, J = 1.9 Hz, 3H), 1.63 ppm (dtd, J = 13.3, 9.4, 6.0 Hz, 1H). 13
C
NMR (101 MHz, CDCl3): δ: 147.7, 146.3, 142.9, 140.5, 135.6, 131.0, 128.6,
128.4, 125.8, 119.2, 108.4, 106.1, 101.0, 41.2, 35.0, 34.1, 32.9, 14.1 ppm.
HRMS (EI): calcd for C20H20O2+: 292.1463, found 292.1458. IR (, cm-1)
3062 (vw), 3026 (w), 2908 (m), 2855 (w), 2778 (vw), 1700 (w), 1684 (w),
1676 (w), 1654 (w), 1604 (w), 1503 (s), 1485 (s), 1443 (s), 1373 (w), 1355
(m), 1308 (w), 1243 (vs), 1217 (s), 1102 (w), 1070 (w), 1038 (vs).
1-Methyl-4-(2-(2-methylallyl)cyclobut-1-en-1-yl)benzene (21a): Using
(2-methylallyl)zinc bromide and 1-iodo-4-methylbenzene according to
general procedure F provided 21a (56 mg, 46%) as pale yellow oil. Rf =
0.8 (hexane, UV, KMnO4, PAA). 1H NMR (400 MHz, CDCl3) δ 7.28 – 7.23
(m, 2H), 7.17 – 7.12 (m, 2H), 4.83 – 4.79 (m, 2H), 3.10 – 3.07 (m, 2H),
2.68 – 2.63 (m, 2H), 2.47 – 2.42 (m, 2H), 2.35 (s, 3H), 1.79 ppm (s, 3H).
13C NMR (101 MHz, CDCl3) δ 142.8, 139.2, 139.1, 136.5, 133.4, 129.1,
1-(2-Methyl-3-phenethylcyclobut-1-en-1-yl)-3-nitrobenzene
(20g):
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