R. Matsubara and T. F. Jamison
FULL PAPERS
glovebox and connected to an argon line. The catalyst mixture was dis-
solved in toluene (2.5 mL) under argon and stirred for 15–30 min at
room temperature. The reaction mixture was purged with ethylene for
1 min to remove argon, taking care not to introduce oxygen. The ethyl-
ene atmosphere was maintained with an ethylene balloon. Triethylamine
(418 mL, 3 mmol, 6 equiv), allylalcohol derivative (0.5 mmol, 1 equiv),
and Et3SiOTf (198 mL, 0.875 mmol, 1.75 equiv) were added in the above
order. The mixture was stirred at room temperature for 20–200 min. The
mixture was then filtered through a plug of silica gel, and washed with a
mixture of hexane/EtOAc (1:1 v/v). The solvents were removed under re-
duced pressure and the crude mixture was purified by silica gel column
chromatography or preparative thin-layer chromatography. The complete
results are summarized in the Supporting Information.
2H); 13C NMR (125 MHz, CDCl3): (E)-isomer: d=159.0, 137.0, 130.5,
129.7, 129.2, 127.6, 114.9, 113.7, 72.4, 69.7, 55.2, 36.7, 33.0 ppm; IR (NaCl
plate, thin film): n˜ =3076, 3000, 2934, 2906, 2854, 1637, 1613, 1586, 1513,
1464, 1441, 1361, 1302, 1248, 1208, 1172, 1098, 1037, 993, 971, 913, 821,
756 cmÀ1
; HRMS-DART: m/z calcd for C15H21O2: 233.1536; found:
233.1534 [M+H]+.
1-Methoxy-4-[(3-vinylpent-4-enyloxy)methyl]benzene (2d-branched)
1H NMR (500 MHz, CDCl3): distinguishable peaks are shown; d=5.71
(ddd, J=7.5, 10.4, 17.2 Hz, 2H), 2.90 ppm (quint, J=7.4 Hz, 1H).
Hexa-2,5-dien-2-ylbenzene (2e)
1H NMR (500 MHz, CDCl3): (E)-isomer: d=7.38–7.41 (m, 2H), 7.28–
7.33 (m, 2H), 7.17–7.26 (m, 1H), 5.89 (ddt, J=10.1, 17.1, 6.2 Hz, 1H),
5.80 (tq, J=7.3, 1.4 Hz, 1H), 5.10 (dq, J=17.1, 1.8 Hz, 1H), 5.02 (dq, J=
10.1, 1.9 Hz, 1H), 2.97 (t, J=7.0 Hz, 2H), 2.04 ppm (d, J=1.4 Hz, 3H);
(Z)-isomer: distinguishable peaks are shown; d=5.49 (tq, J=7.6, 1.5 Hz,
1H), 2.72 ppm (ddq, J=6.1, 6.1, 1.4 Hz, 2H); 13C NMR (125 MHz,
CDCl3): (E)-isomer: d=143.7, 136.6, 135.9, 128.1, 126.6, 125.6, 125.2,
114.8, 33.0, 15.8 ppm; IR (NaCl plate, thin film): n˜ =3079, 3058, 3031,
(E)-Penta-1,4-dienylbenzene (2a)
1H NMR (500 MHz, CDCl3): d=7.16–7.36 (m, 5H), 6.41 (d, J=15.9 Hz,
1H), 6.22 (dt, J=6.7, 15.9 Hz, 1H), 5.90 (dtt, J=6.4, 10.1, 17.0 Hz, 1H),
5.11 (dq, J=1.9, 17.1 Hz, 1H), 5.06 (dq, J=1.4, 10.1 Hz, 1H), 2.96 ppm
(dt, J=1.5, 6.6 Hz, 2H); 13C NMR (125 MHz, CDCl3): d=137.5, 136.4,
130.8, 128.5, 128.1, 127.0, 126.0, 115.6, 37.0ppm; IR (NaCl plate, thin
film): n˜ =3080, 3060, 3026, 2978, 2891, 1944, 1637, 1599, 1495, 1448, 1429,
2977, 2922, 1637, 1598, 1493, 1444, 1379, 1026, 993, 910, 756, 695 cmÀ1
;
1305, 992, 965, 914, 742, 692 cmÀ1
.
HRMS-EI: m/z calcd for C12H14: 158.1090; found: 158.1094 [M]+.
(1E)-Penta-1,3-dienylbenzene (3a)
(2E)-Hexa-2,4-dien-2-ylbenzene (3c)
1H NMR (500 MHz, CDCl3): d=distinguishable peaks are shown.
(1E,3E)-isomer: d=6.74 (dd, J=10.5, 15.7 Hz, 1H), 1.82 ppm (dd, J=
1.1, 6.8 Hz, 3H); (1E,3Z)-isomer: d=1.86 ppm (dd, J=1.7, 7.2 Hz, 3H).
1H NMR (500 MHz, CDCl3): distinguishable peaks are shown; d=
1.86 ppm (d, J=6.7 Hz, 3H).
(E)-Hexa-2,5-dien-3-ylbenzene (3d)
(1E)-Hepta-1,3,6-trienylbenzene (2b)
1H NMR (500 MHz, CDCl3): distinguishable peaks are shown; d=3.26
(d, J=5.9 Hz, 2H), 1.79 ppm (d, J=6.9 Hz, 3H).
1H NMR (500 MHz, CDCl3): (1E,3E)-isomer: d=7.16–7.42 (m, 5H), 6.76
(dd, J=10.5, 15.7 Hz, 1H), 6.46 (d, J=15.7 Hz, 1H), 6.22 (dd, J=10.5,
15.2 Hz, 1H), 5.77–5.91 (m, 2H), 5.07 (dq, J=1.6, 17.2 Hz, 1H), 5.02–
5.06 (m, 1H), 2.89 ppm (dt, J=1.3, 6.7 Hz, 2H); (1E,3Z)-isomer: distin-
guishable peaks are shown; d=7.04 (ddd, J=1.2, 11.1, 15.6 Hz, 1H), 6.54
(d, J=15.6 Hz, 1H), 5.10 (dq, J=1.8, 17.1 Hz, 1H), 5.53 ppm (dt, J=7.7,
10.7 Hz, 1H); 13C NMR (125 MHz, CDCl3): (1E,3E)-isomer: d=137.5,
136.3, 132.6, 131.5, 130.7, 129.0, 128.5, 127.2, 126.2, 115.6, 36.8; (1E,3Z)-
isomer: d=137.4, 136.3, 132.7, 129.7, 129.4, 128.5, 127.5, 126.3, 124.0,
115.3, 32.1 ppm; IR (NaCl plate, thin film): n˜ =3079, 3060, 3023, 2910,
1944, 1844, 1680, 1637, 1596, 1495, 1448, 1428, 1295, 988, 913, 746,
691 cmÀ1; HRMS-DART: m/z calcd for C13H15: 171.1168; found: 171.1171
[M+H]+.
(2-Methylpenta-1,4-dienyl)benzene (2 f)
1H NMR (500 MHz, CDCl3): (E)-isomer: d=7.27–7.33 (m, 2H), 7.21–
7.26 (m, 2H), 7.16–7.20 (m, 1H), 6.30 (s, 1H), 5.88 (ddt, J=10.1, 17.0,
6.9 Hz, 1H), 5.07–5.15 (m, 2H), 2.90 (d, J=6.9 Hz, 2H), 1.85 ppm (d, J=
1.3 Hz, 3H); (Z)-isomer: distinguishable peaks are shown; d=6.39 (s,
1H), 2.96 (d, J=6.2 Hz, 2H), 1.88 ppm (d, J=1.5 Hz, 3H); 13C NMR
(125 MHz, CDCl3): (E)-isomer: d=138.4, 137.2, 136.4, 128.8, 128.0,
125.9, 125.7, 116.3, 45.0, 17.8; (Z)-isomer: distinguishable peaks are
shown; d=115.9, 37.2, 28.0 ppm; IR (NaCl plate, thin film): n˜ =3079,
3023, 2977, 2911, 1653, 1635, 1492, 1441, 1383, 1172, 1073, 993, 915, 830,
742, 698 cmÀ1
158.1092 [M]+.
; HRMS-EI: m/z calcd for C12H14: 158.1090; found:
Hepta-1,3,5-trienylbenzene (3b)
1H NMR (500 MHz, CDCl3): distinguishable peaks are shown; d=
1.79 ppm (dd, J=1.5, 6.8 Hz, 3H).
(E)-(3-Methylpenta-1,4-dienyl)benzene (2g)
1H NMR (500 MHz, CDCl3): d=7.16–7.36 (m, 5H), 6.36 (d, J=16.0 Hz,
1H), 6.17 (dd, J=7.1, 16.0 Hz, 1H), 5.86 (ddd, J=6.6, 10.3, 17.0 Hz, 1H),
5.07 (dt, J=17.0, 1.5 Hz, 1H), 5.01 (dt, J=10.3, 1.4 Hz, 1H), 2.97–3.07
(m, 1H), 1.19 ppm (d, J=6.9 Hz, 3H); 13C NMR (125 MHz, CDCl3): d=
142.4, 137.6, 134.2, 128.6, 128.4, 127.0, 126.0, 113.3, 40.6, 19.8 ppm; IR
(NaCl plate, thin film): n˜ =3081, 3060, 3026, 2966, 2927, 2869, 1635, 1599,
1495, 1448, 1411, 1369, 994, 965, 913, 747, 692 cmÀ1; HRMS-EI: m/z calcd
for C12H14: 158.1090; found: 158.1089 [M]+.[43]
tert-Butyl(hepta-3,6-dienyloxy)dimethylsilane (2c-linear)
1H NMR (500 MHz, CDCl3): (E)-isomer: d=5.82 (ddt, J=6.4, 10.4,
17.0 Hz, 1H), 5.40–5.55 (m, 2H), 5.02 (dq, J=1.7, 17.1 Hz, 1H), 4.98 (dd,
J=1.3, 10.1 Hz, 1H), 3.62 (t, J=6.9 Hz, 2H), 2.75 (t, J=6.1 Hz, 2H),
2.23 (q, J=6.7 Hz, 2H), 0.89 (s, 9H), 0.05 ppm (s, 6H); (Z)-isomer: dis-
tinguishable peaks are shown; d=2.81 ppm (t, J=6.1 Hz, 2H); 13C NMR
(125 MHz, CDCl3): (E)-isomer: d=137.1, 129.8, 127.8, 114.9, 63.2, 36.8,
36.3, 25.9, 18.4, À5.2 ppm; IR (NaCl plate, thin film): n˜ =2929, 2858,
1472, 1255, 1102, 968, 912, 836, 775 cmÀ1; HRMS-DART: m/z calcd for
C13H27OSi: 227.1826; found: 227.1829 [M+H]+.
(E)-Buta-1,3-dienylbenzene (3e) was previously reported.
Gram-Scale ASR of Ethylene
A round-bottomed flask and a stirrer bar were oven-dried and put into a
glovebox. [NiACHTNUGTRENNUG(cod)2] (68.8 mg, 0.25 mmol, 2.5 mol%) and PACHTUNGTRENNUNG(o-anisyl)3
tert-Butyldimethyl(3-vinylpent-4-enyloxy)silane (2c-branched)
1H NMR (500 MHz, CDCl3): distinguishable peaks are shown; d=5.73
(ddd, J=7.5, 10.5, 17.4 Hz, 2H), 2.89 ppm (quint, J=7.3 Hz, 1H).
(352 mg, 1 mmol, 10 mol%) were added to the flask, which was sealed
with a septum; the flask was taken out of the glovebox and connected to
an argon line. The catalyst mixture was dissolved in toluene (50 mL)
under argon and stirred for 15 min at room temperature. The reaction
mixture was purged with ethylene for 1 min to remove argon, taking care
not to introduce oxygen. The ethylene atmosphere was maintained with
an ethylene balloon. Triethylamine (8.4 mL, 60 mmol, 6 equiv), cinnamyl
methylcarbonate (10 mmol, 1 equiv), and Et3SiOTf (4.0 mL, 17.5 mmol,
1.75 equiv) were added in the above order. The mixture was stirred at
1-[(Hepta-3,6-dienyloxy)methyl]-4-methoxybenzene (2d-linear)
1H NMR (500 MHz, CDCl3): (E)-isomer: d=7.26 (d, J=8.8 Hz, 2H),
6.87 (d, J=8.8 Hz, 2H), 5.81 (ddt, J=6.4, 10.1, 17.2 Hz, 1H), 5.42–5.55
(m, 2H), 4.96–5.05 (m, 2H), 4.44 (s, 2H), 3.79 (s, 3H), 3.46 (t, J=6.9 Hz,
2H), 2.75 (t, J=5.7 Hz, 2H), 2.32 ppm (dq, J=0.7, 6.9 Hz, 2H); (Z)-
isomer: distinguishable peaks are shown; d=2.81 ppm (t, J=5.7 Hz,
1870
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2011, 6, 1860 – 1875