8034
R.M. Denton et al. / Tetrahedron 66 (2010) 8029e8035
ArOCH3), 3.38 (2H, d, J¼6.7, ArCH2CHCH2). 13C NMR: (100 MHz,
nmax (CHCl3) 3594, 3556, 3082, 3060, 2979, 2905, 1639, 1611, 1516,
1493, 1331, 1260, 1171, 911, 839 cmꢁ1 1H NMR: (400 MHz, CDCl3)
CDCl3)
d
154.9 (Cq), 154.5 (Cq), 137.8 (CH), 132.3 (Cq), 131.2 (Cq),
.
131.0 (CH), 130.8 (CH), 130.2 (Cq), 128.1 (CH), 115.6 (CH2),114.9 (CH),
111.3 (CH), 55.7 (CH3), 39.4 (CH2). HRMS: (ESIþ) m/z calculated for
C16H16O2Na 263.1039, m/z found 263.1043.
d
7.36 (2H, d, J¼8.4, ArHmeta), 7.07 (1H, dd, J¼8.0, 2.0, ArHmeta), 7.04
(1H, d, J¼2.0, ArHmeta), 6.95 (2H, d, J¼8.4, ArHmeta), 6.92 (1H, d,
J¼8.0, ArHortho), 5.99 (1H, ddt, J¼16.8, 10.0, 6.8, ArCH2CHCH2), 5.21
(1H, br s, ArOH), 5.10 (1H, dd, J¼16.8, 1.6, ArCH2CHCH2trans),
5.07 (1H, dd, J¼10.0, 1.6, ArCH2CHCH2cis), 3.36 (2H, d, J¼6.8,
5.9. 5-Allyl-40-(allyloxy)-2-methoxybiphenyl 18
ArCH2CHCH2). 13C NMR: (100 MHz, CDCl3)
d 39.4 (CH2), 115.6 (CH),
To a solution of 16 (250 mg, 1.04 mmol) in acetone (5 mL) were
added K2CO3 (216 mg, 1.56 mmol) and allyl bromide (0.996 mL,
1.14 mmol) and the solution was heated to reflux for 18 h. The re-
action was cooled to room temperature and MeOH (10 mL) was
added. The reaction was stirred for a further 15 min before the
reaction was diluted with EtOAc (20 mL), washed with brine
(3ꢂ20 mL), dried over MgSO4 and concentrated in vacuo giving 18
(278 mg, 99%) as a colourless oil, Rf 0.68 (petrol/EtOAc, 3:1). IR: nmax
(CHCl3) 3072, 3009, 2960, 2938, 1736, 1670, 1639, 1515, 1495, 1266,
115.7 (CH2), 116.1 (CH), 127.7 (Cq), 128.9 (CH), 129.5 (Cq), 130.3
(CH), 130.5 (CH), 132.4 (Cq), 137.8 (CH), 150.8 (Cq), 155.3 (Cq).
HRMS: (ESIþ) m/z calculated for C15H14O2Na 249.0891, m/z found
249.0907.
Acknowledgements
This work was financially supported by The University of Not-
tingham (New Researcher’s Fund NF5012) and the Royal Society
(Research Grant RG090319).
1240, 1179, 1029, 997, 834 cmꢁ1. 1H NMR: (400 MHz, CDCl3)
d 7.49
(2H, d, J¼8.8, ArHmeta), 7.16 (1H, d, J¼2.0, ArHmeta), 7.13 (1H, dd,
J¼8.4, 2,0, ArHmeta), 6.99 (2H, d, J¼8.8, ArHortho), 6.93 (1H, d, J¼8.4,
ArHortho), 6.11 (1H, ddt, J¼17.2, 10.4, 5.2, ArOCH2CHCH2), 6.00 (1H,
ddt, J¼16.8, 10.0, 6.8, ArCH2CHCH2), 5.47 (1H, dd, J¼17.2, 1.2,
ArOCH2CHCH2trans), 5.33 (1H, dd, J¼10.4, 1.2, ArOCH2CHCH2cis), 5.12
(1H, dd, J¼16.8, 1.6, ArCH2CHCH2trans), 5.09 (1H, dd, J¼10.0, 1.6,
ArCH2CHCH2cis), 4.60 (2H, d, J¼5.2, ArOCH2CHCH2), 3.84 (3H, s,
ArOCH3), 3.40 (2H, d, J¼6.8, ArCH2CHCH2). 13C NMR: (100 MHz,
Supplementary data
Supplementary data associated with this article can be found in
References and notes
CDCl3)
d 157.7 (Cq), 154.9 (Cq), 137.8 (CH), 133.5 (Cq), 132.3 (Cq),
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115.6 (CH2),114.3 (CH),111.4 (CH), 68.9 (CH2), 55.7 (CH3), 39.5 (CH2).
HRMS: (ESIþ) m/z calculated for C19H20O2H 286.1536, m/z found
286.1522.
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(1.5 mL) was heated at 200 ꢀC for 15 min using a microwave. Pu-
rification by flash chromatography (gradial elution starting with
petrol increasing to petrol/EtOAc, 5:1) gave 19 (17.2 mg, 86%) as
a colourless oil, Rf 0.36 (petrol/EtOAc, 4:1). IR: nmax (CHCl3) 3599,
3080, 3010, 2955, 2936, 2908, 2838, 1639, 1611, 1585, 1512, 1466,
1435, 1301, 1247, 1176, 1035, 919 cmꢁ1. 1H NMR: (400 MHz, CDCl3)
d
7.32 (1H, dd, J¼8.2, 2.1, ArHmeta), 7.29 (1H, d, J¼2.0, ArHmeta), 7.12
(1H, s, ArHmeta), 7.11 (1H, dd, J¼8.1, 2.4, ArHmeta), 6.91 (1H, d, J¼8.1,
ArHortho), 6.86 (1H, d, J¼8.2, ArHortho), 6.12e5.94 (2H, m,
ArCH2CHCH2), 5.23 (1H, dd, J¼17.3, 1.6, ArCH2CHCH2trans), 5.19 (1H,
dd, J¼11.5, 1.6, ArCH2CHCH2cis), 5.11 (1H, dd, J¼17.2, 1.6, ArCH2-
CHCH2trans), 5.07 (1H, dd, J¼11.3, 1.6, ArCH2CHCH2cis), 5.04 (1H, br s,
ArOH), 3.80 (3H, s, ArOCH3), 3.47 (2H, d, J¼6.4, ArCH2CHCH2), 3.38
(2H, d, J¼6.8, ArCH2CHCH2). 13C NMR: (100 MHz, CDCl3)
d 154.8
(Cq), 153.3 (Cq). 137.8 (CH), 136.5 (CH), 132.3 (Cq), 131.5 (CH), 131.2
(Cq), 131.0 (CH), 130.4 (Cq), 129.0 (CH), 128.0 (CH), 124.7 (Cq), 116.6
(CH2),115.5 (CH2), 115.4 (CH), 111.3 (CH), 55.7 (CH3), 39.4 (CH2), 35.4
(CH2). HRMS: (ESIþ) m/z calculated for C19H20O2Na 303.1356, m/z
found 303.1356.
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5.11. 5-Allylbiphenyl-2,40-diol 20
To a solution of 18 (200 mg, 0.713 mmol) in DCE (5 mL) was
added BCl3$SMe2 (1.12 mL, 1.78 mmol of a 2.00 M solution in
CH2Cl2) and the solution was heated to reflux for 18 h. The re-
action was cooled to room temperature and H2O (5 mL) was
added. The reaction was stirred for a further 15 min before being
diluted with CH2Cl2 (20 mL), washed with brine (3ꢂ20 mL), dried
over MgSO4 and concentrated in vacuo. Purification by flash
chromatography (petrol/EtOAc, 3:1) also gave 22 (94.9 mg, 49%) as
a colourless solid, mp 104e106 ꢀC, Rf 0.22 (petrol/EtOAc, 3:1). IR:
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16. For a similar lithiation on a diethylcarbamate, see Ref. 1d.