One-Pot Bromination and Carbon–Carbon Bond-Formation
4.55 (dd, J = 1.7, 1.7 Hz, 2 H), 5.38 (dt, J = 1.7, 1.7 Hz, 1 H), 5.43
(dt, J = 1.7, 1.7 Hz, 1 H), 7.22–7.42 (m, 4 H), 7.55 (m, 1 H) ppm.
Arene 5s: IR (neat): ν = 3054, 2962, 2931, 2862, 2360, 2337, 1597,
˜
1489, 1458, 1350, 1089 cm–1. 1H NMR (300 MHz, CDCl3): δ =
13C NMR (126 MHz, CDCl3): δ = 12.1 (ϫ3), 18.0 (ϫ6), 64.8, 0.86 (t, J = 7.4 Hz, 3 H), 1.39 (qt, J = 7.4, 7.4 Hz, 2 H), 2.03 (dt,
111.0, 126.0 (ϫ2), 127.6, 128.3 (ϫ2), 139.3, 147.0 ppm. HRMS
(ESI): [M + Na]+ calcd. for C18H30OSiNa [M + Na]+ 313.1958;
found 313.1961.
J = 7.7, 7.4 Hz, 2 H), 4.14 (s, 2 H), 4.40 (s, 2 H), 5.74 (m, 1 H),
7.10–7.38 (m, 9 H) ppm. 13C NMR (126 MHz, CDCl3): δ = 13.8,
23.0, 30.7, 70.8, 75.3, 126.8, 128.1 (ϫ2), 128.4 (ϫ2), 128.6 (ϫ2),
129.0 (ϫ2), 131.3, 133.1, 137.0, 137.1, 139.0 ppm. HRMS (ESI):
[M + Na]+ calcd. for C19H21ClONa [M + Na]+ 323.1173; found
323.1175.
Arene 5m: IR (neat): ν = 3000, 2931, 2908, 2854, 1612, 1589, 1512,
˜
1458, 1358, 1304, 1250, 1173, 1080 cm–1. 1H NMR (500 MHz,
CDCl3): δ = 3.81 (s, 3 H), 4.27 (s, 2 H), 4.48 (s, 2 H), 5.25 (s, 1 H),
5.69 (s, 1 H), 6.37–6.40 (m, 2 H), 6.88 (d, J = 8.6 Hz, 2 H), 7.27
(d, J = 8.6 Hz, 2 H), 7.37 (d, J = 1.2 Hz, 1 H) ppm. 13C NMR
(126 MHz, CDCl3): δ = 55.3, 70.2, 71.5, 107.0, 111.2, 111.7, 113.8
(ϫ2), 129.5 (ϫ2), 130.2, 134.2, 141.9, 152.7, 159.2 ppm. HRMS
(ESI): [M + Na]+ calcd. for C15H16O3Na [M + Na]+ 267.0992;
found 267.0992.
Arene 5t: IR (neat): ν = 2954, 2862, 2337, 1466, 1381, 1250,
˜
1
1119 cm–1. H NMR (300 MHz, CDCl3): δ = 0.85 (t, J = 7.4 Hz,
3 H), 0.99–1.16 (m, 21 H), 1.37 (tq, J = 7.5, 7.4 Hz, 2 H), 1.96 (td,
J = 7.5, 7.4 Hz, 2 H), 4.37 (m, 2 H), 5.81 (m, 1 H), 7.08–7.19 (m,
2 H), 7.22–7.36 (m, 3 H) ppm. 13C NMR (126 MHz, CDCl3): δ =
12.1 (ϫ3), 13.8, 18.0 (ϫ6), 23.1, 30.3, 67.3, 126.0, 126.7, 128.0
(ϫ2), 128.7 (ϫ2), 139.4, 139.8 ppm. HRMS (ESI): [M + Na]+
calcd. for C21H36OSiNa [M + Na]+ 355.2428; found 355.2427.
Arene 5n: IR (neat): ν = 2931, 2862, 1612, 1512, 1458, 1296, 1250,
˜
1
1173, 1111, 1080 cm–1. H NMR (500 MHz, CDCl3): δ = 3.81 (s,
3 H), 4.34 (s, 2 H), 4.51 (s, 2 H), 5.25 (s, 1 H), 5.57 (s, 1 H), 6.88
(d, J = 8.5 Hz, 2 H), 6.98 (dd, J = 4.9, 3.9 Hz, 1 H), 7.14 (d, J =
3.9 Hz, 1 H), 7.19 (d, J = 4.9 Hz, 1 H), 7.27 (d, J = 8.5 Hz, 2 H)
ppm. 13C NMR (126 MHz, CDCl3): δ = 55.3, 71.6, 71.8, 113.1,
113.8 (ϫ2), 124.1, 124.5, 127.3, 129.5 (ϫ2), 130.2, 138.2, 142.5,
159.3 ppm. HRMS (ESI): [M + Na]+ calcd. for C15H16O2SNa [M
+ Na]+ 283.0763; found 283.0760.
Arene 5u: IR (neat): ν = 3055, 2954, 2854, 2337, 1466, 1365, 1265,
˜
1
1111 cm–1. H NMR (300 MHz, CDCl3): δ = 0.86 (t, J = 7.4 Hz,
3 H), 1.04 (s, 9 H), 1.38 (tq, J = 7.5, 7.4 Hz, 2 H), 1.96 (td, J =
7.5, 7.2 Hz, 2 H), 4.33 (d, J = 1.3 Hz, 2 H), 5.84 (tt, J = 7.2, 1.3 Hz,
1 H), 7.05–7.11 (m, 2 H), 7.18–7.45 (m, 9 H), 7.62–7.68 (m, 4 H)
ppm. 13C NMR (126 MHz, CDCl3): δ = 13.8, 19.3, 23.1, 26.8 (ϫ3),
30.4, 68.0, 126.7, 127.0, 127.6 (ϫ4), 127.9 (ϫ2), 128.8 (ϫ2), 129.5
(ϫ2), 133.7 (ϫ2), 135.6 (ϫ4), 139.2, 139.5 ppm. HRMS (ESI): [M
+ Na]+ calcd. for C28H34OSiNa [M + Na]+ 433.2271; found
437.2271.
Arene 5o: IR (neat): ν = 3001, 2931, 2854, 1712, 1604, 1512, 1458,
˜
1304, 1250, 1173, 1080 cm–1. 1H NMR (500 MHz, CDCl3): δ =
3.81 (s, 3 H), 4.36 (s, 2 H), 4.49 (s, 2 H), 5.52 (s, 1 H), 5.74 (s, 1
H), 6.88 (d, J = 8.5 Hz, 2 H), 7.23 (d, J = 8.5 Hz, 2 H), 7.35 (d, J
= 5.8 Hz, 2 H), 8.56 (d, J = 5.8 Hz, 2 H) ppm. 13C NMR
(126 MHz, CDCl3): δ = 55.3, 70.9, 71.8, 113.8 (ϫ2), 117.9, 120.7
(ϫ2), 129.5 (ϫ2), 129.8, 142.3, 140.6, 149.9 (ϫ2), 159.4 ppm.
HRMS (ESI): [M + H]+ calcd. for C16H18NO2: 256.1332; found
256.1334.
Arene 5v: IR (neat): ν = 2954, 2931, 2862, 1612, 1512, 1458, 1250,
˜
1
1173, 1095, 1072 cm–1. H NMR (500 MHz, CDCl3): δ = 0.86 (t,
J = 7.3 Hz, 3 H), 1.41 (qt, J = 7.5, 7.3 Hz, 2 H), 2.07 (dt, J = 7.6,
7.5 Hz, 2 H), 3.78 (s, 3 H), 4.27 (s, 2 H), 4.47 (s, 2 H), 5.83 (t, J =
7.6 Hz, 1 H), 6.82 (d, J = 8.6 Hz, 2 H), 7.19 (d, J = 8.6 Hz, 2 H),
7.36 (m, 1 H), 7.42–7.50 (m, 2 H), 7.67 (s, 1 H), 7.76–7.86 (m, 3
H) ppm. 13C NMR (126 MHz, CDCl3): δ = 13.8, 23.0, 30.8, 55.3,
71.4, 74.9, 113.7 (ϫ2), 125.6, 125.9, 127.1, 127.4, 127.5, 127.6,
127.9, 129.3 (ϫ2), 130.5, 131.5, 132.4, 133.3, 136.8, 137.4,
159.1 ppm. HRMS (ESI): [M + Na]+ calcd. for C24H26O2Na [M +
Na]+ 369.1825; found 369.1826.
Arene 5p: m.p. 66.2–66.5 °C. IR (neat): ν = 3024, 2954, 2931, 2854,
˜
1612, 1512, 1450, 1304, 1250, 1126, 1103, 1034 cm–1. 1H NMR
(500 MHz, CDCl3): δ = 3.81 (s, 3 H), 4.28 (s, 2 H), 4.50 (s, 2 H),
5.33 (s, 1 H), 5.34 (s, 1 H), 6.69 (d, J = 16.9 Hz, 1 H), 6.81 (d, J =
16.9 Hz, 1 H), 6.89 (d, J = 8.2 Hz, 2 H), 7.23 (dd, J = 7.0, 7.0 Hz,
1 H), 7.28–7.34 (m, 4 H), 7.41 (d, J = 8.2 Hz, 2 H) ppm. 13C NMR
(126 MHz, CDCl3): δ = 55.3, 70.0, 71.7, 113.8 (ϫ2), 118.0, 126.5
(ϫ2), 127.6, 128.5, 128.6 (ϫ2), 129.2, 129.5 (ϫ2), 130.4, 134.3,
137.2, 142.4 ppm. HRMS (ESI): [M + Na]+ calcd. for C19H20O2Na
[M + Na]+ 303.1356; found 303.1352.
Arene 5w: IR (neat): ν = 2954, 2931, 2862, 1612, 1527, 1466, 1350,
˜
1
1250, 1173, 1080 cm–1. H NMR (500 MHz, CDCl3): δ = 0.96 (t,
J = 7.3 Hz, 3 H), 1.50 (qt, J = 7.3, 7.3 Hz, 2 H), 2.24 (dt, J = 7.4,
7.3 Hz, 2 H), 3.81 (s, 3 H), 4.38 (s, 2 H), 4.47 (s, 2 H), 6.10 (t, J =
7.4 Hz, 1 H), 6.87 (d, J = 8.6 Hz, 2 H), 7.23 (d, J = 8.6 Hz, 2 H),
7.45 (dd, J = 8.4, 7.8 Hz, 1 H), 7.74 (d, J = 7.8 Hz, 1 H), 8.08 (dd,
J = 8.4, 2.1 Hz, 1 H), 8.28 (s, 1 H) ppm. 13C NMR (126 MHz,
CDCl3): δ = 13.8, 22.8, 30.6, 55.3, 65.8, 72.0, 113.9 (ϫ2), 121.2,
121.5, 129.0, 129.5 (ϫ2), 129.9, 132.2, 134.6, 136.1, 143.3, 148.3,
159.3 ppm. HRMS (ESI): [M + Na]+ calcd. for C20H23NO4Na [M
+ Na]+ 364.1519; found 364.1515.
Arene 5q: m.p. 68.3–71.4 °C. IR (neat): ν = 2854, 1612, 1589, 1512,
˜
1450, 1358, 1250, 1180, 1103, 1065, 1026 cm–1. 1H NMR
(500 MHz, CDCl3): δ = 3.80 (s, 3 H), 4.50 (s, 2 H), 4.53 (s, 2 H),
5.46 (s, 1 H), 5.69 (s, 1 H), 6.87 (d, J = 8.4 Hz, 2 H), 7.26 (d, J =
8.4 Hz, 2 H), 7.40–7.49 (m, 2 H), 7.63 (d, J = 8.4 Hz, 1 H), 7.76–
7.83 (m, 3 H), 7.89 (s, 1 H) ppm. 13C NMR (126 MHz, CDCl3): δ
= 55.3, 71.6, 71.8, 113.8 (ϫ2), 115.1, 124.4, 125.0, 125.9, 126.1,
127.5, 127.8, 128.3, 129.4 (ϫ2), 130.3, 133.0, 133.4, 136.0, 144.1,
159.2 ppm. HRMS (ESI): [M + Na]+ calcd. for C21H20O2Na [M +
Na]+ 327.1356; found 327.1352.
Arene 5x: IR (neat): ν = 2962, 2931, 2862, 1612, 1512, 1458, 1365,
˜
1
1250, 1173, 1080 cm–1. H NMR (500 MHz, CDCl3): δ = 1.04 (d,
J = 6.5 Hz, 6 H), 2.71 (m, 1 H), 3.80 (s, 3 H), 4.36 (s, 2 H), 4.47
(s, 2 H), 5.94 (d, J = 9.8 Hz, 1 H), 6.87 (d, J = 8.5 Hz, 2 H), 6.95
(dd, J = 4.6, 3.6 Hz, 1 H), 7.07 (d, J = 3.6 Hz, 1 H), 7.11 (d, J =
4.6 Hz, 1 H), 7.25 (d, J = 8.5 Hz, 2 H) ppm. 13C NMR (126 MHz,
CDCl3): δ = 23.2 (ϫ2), 27.6, 55.3, 66.5, 71.5, 113.7 (ϫ2), 123.2,
123.3, 127.2, 128.0, 129.5 (ϫ2), 130.4, 139.7, 145.4, 159.2 ppm.
HRMS (ESI): [M + Na]+ calcd. for C18H22O2SNa [M + Na]+
325.1233; found 325.1230.
Arene 5r: IR (neat): ν = 2954, 2931, 2862, 1612, 1512, 1458, 1250,
˜
1
1173 cm–1. H NMR (500 MHz, CDCl3): δ = 0.86 (t, J = 7.3 Hz,
3 H), 1.39 (qt, J = 7.3, 7.3 Hz, 2 H), 2.02 (dt, J = 7.3, 7.3 Hz, 2
H), 3.77 (s, 3 H), 4.18 (s, 2 H), 4.44 (s, 2 H), 5.75 (t, J = 7.3 Hz, 1
H), 6.84 (d, J = 8.7 Hz, 2 H), 7.16–7.35 (m, 7 H) ppm. 13C NMR
(126 MHz, CDCl3): δ = 13.8, 23.0, 30.7, 55.2, 71.3, 74.8, 113.7
(ϫ2), 126.7, 128.0 (ϫ2), 128.6 (ϫ2), 129.3 (ϫ2), 130.5, 130.8,
137.3, 139.2, 159.1 ppm. HRMS (ESI): [M + Na]+ calcd. for
C20H24O2Na [M + Na]+ 319.1669; found 319.1670.
Supporting Information (see footnote on the first page of this arti-
1
cle): Copies of H and 13C NMR spectra of final products.
Eur. J. Org. Chem. 2013, 3337–3346
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3345