4282
D. Garc´ıa et al. / Tetrahedron 64 (2008) 4275e4286
(2H, m, ArH), 7.33e7.37 (1H, m, ArH), 7.38e7.43 (3H, m,
ArH); dC 16.0 (CH3), 62.3 (CH2O), 125.7, 126.9, 127.0, 128.2,
129.5, 129.7, 133.8, 139.3, 142.2, 143.0 (ArC); m/z 198 (Mþ,
48%), 181 (10), 180 (51), 179 (30), 178 (14), 166 (20), 165
(100), 155 (23), 154 (11), 153 (13), 152 (22), 89 (11).
4.7.6. 1-[3-(Hydroxymethyl)biphenyl-4-yl]-3,3-dimethyl-
butan-2-ol (18b)
White solid; mp 113e114 ꢁC (hexane/dichloromethane);
Rf¼0.42 (hexane/ethyl acetate 2:1); n (KBr) 3241 cmꢀ1 (OH);
dH 0.97 (9H, s, C(CH3)3), 2.68e2.82 (2H, m, CH2CH), 3.33
(1H, dd, J¼7.5, 2.5 Hz, CHOH), 3.74 (2H, br s, 2ꢂOH), 4.38
(2H, d, J¼11.8 Hz, CHHOH), 4.79 (2H, d, J¼11.8 Hz,
CHHOH), 7.21 (1H, d, J¼8.3 Hz, ArH), 7.32e7.55 (5H, m,
ArH), 7.56 (2H, dd, J¼3.3, 1.4 Hz, ArH); dC 25.8 (CH3), 33.7
(C), 35.4 (CH2), 63.5 (CH2OH), 81.4 (CHOH), 127.1, 128.8,
128.9, 130.7, 138.6, 139.4, 139.9, 140.8 (ArC); m/z 266
[(MþꢀH2O), 4%], 181 (60), 180 (100), 179 (12), 178 (11),
167 (15), 165 (24), 152 (12); HRMS: MþꢀH2O, found:
266.1666, C19H22O requires: 266.1671.
4.7.2. 1-[3-(Hydroxymethyl)biphenyl-2-yl]-3,3-dimethyl-
butan-2-ol (17b)
White solid; mp 111e112 ꢁC (hexane/dichloromethane);
Rf¼0.34 (hexane/ethyl acetate 2:1); n (KBr) 3322 (OH),
1362 cmꢀ1 (CO); dH 0.59 (9H, s, C(CH3)3), 2.62e2.70 (1H,
m, CHHCH), 2.99 (1H, d, J¼10.4 Hz, CHHCH), 3.11 (1H,
d, J¼10.4 Hz, CHOH), 3.62 (2H, br s, 2ꢂOH), 4.44 (1H, d,
J¼11.7 Hz, CHHOH), 4.88 (1H, d, J¼11.7 Hz, CHHOH),
7.19e7.40 (8H, m, ArH); dC 25.2 (CH3), 30.3 (CH2), 35.0
(C), 64.0 (CH2OH), 79.2 (CHOH), 126.4, 127.1, 128.3,
129.5, 130.1, 130.6, 136.7, 140.4, 142.2, 143.3 (ArC); m/z
266 (MþꢀH2O, 2%), 181 (37), 180 (100), 179 (21), 178
(15), 167 (14), 166 (20), 165 (63), 152 (11); HRMS:
MþꢀH2O, found: 266.1675, C19H22O requires: 266.1671.
4.7.7. 2-[3-(Hydroxymethyl)biphenyl-4-yl]-1-phenyl-
ethanol (18c)
White solid; mp 109e110 ꢁC (hexane/dichloromethane);
Rf¼0.30 (hexane/ethyl acetate 2:1); n (KBr) 3394 (OH), 3063,
3018 cmꢀ1 (ArH); dH 3.08e3.16 (2H, m, CH2CH), 3.72 (2H,
br s, 2ꢂOH), 4.52 (1H, d, J¼8.9 Hz, CHHOH), 4.81 (1H, d,
J¼8.9 Hz, CHHOH), 4.89 (1H, dd, J¼4.5, 2.4 Hz, CHOH),
7.25e7.45 (8H, m, ArH), 7.50e7.59 (5H, m, ArH); dC 42.1
(CH2), 63.6 (CH2OH), 75.7 (CHOH), 125.8, 127.2, 127.2,
127.4, 127.9, 128.7, 128.9, 129.0, 131.2, 136.5, 140.0, 140.7,
144.3 (ArC); m/z 286 [(Mþꢀ18), 4%], 181 (17), 180 (100),
165 (11); HRMS: MþꢀH2O, found: 286.1362, C21H18O re-
quires: 286.1358.
4.7.3. 2-[3-(Hydroxymethyl)biphenyl-2-yl]-1-phenyl-
ethanol (17c)
Yellow oil; Rf¼0.23 (hexane/ethyl acetate 2:1); n (film) 3355
(OH), 1257 cmꢀ1 (CO); dH 2.93e3.19 (2H, m, CH2CH), 3.43
(2H, br s, 2ꢂOH), 4.39e4.42 (1H, m, CHHOH), 4.66 (1H, br
s, CHOH), 4.80e4.85 (1H, m, CHHOH), 6.76e7.46 (13H, m,
ArH); dC 39.5, 39.7 (CH2), 63.8, 63.9 (CH2OH), 78.2, 79.2
(CHOH), 125.4, 126.7, 126.9, 127.1, 127.2, 127.4, 127.9,
128.2, 128.3, 128.4, 128.6, 128.7, 129.3, 129.4, 129.6, 130.7,
139.9, 140.0 (ArC); m/z 195 (MþꢀPhCHO, 2%), 108 (99),
107 (100), 105 (11), 79 (88), 78 (11), 77 (57), 51 (12); HRMS:
MþꢀH2O, found: 286.1354, C21H18O requires: 286.1358.
4.7.8. 3-{[3-(Hydroxymethyl)biphenyl-4-yl]methyl}pentan-
3-ol (18d)
Yellow oil; Rf¼0.26 (hexane/ethyl acetate 2:1); n (film) 3342
(OH), 3029 cmꢀ1 (ArH); dH 0.97 (6H, t, J¼7.5 Hz, 2ꢂCH3),
1.57e1.63 (4H, m, 2ꢂCH2CH3), 2.92 (2H, s, ArCH2COH),
3.37 (2H, br s, 2ꢂOH), 4.67 (2H, s, CH2OH), 7.22 (1H, d,
J¼7.9 Hz, ArH), 7.33e7.50 (4H, m, ArH), 7.58e7.61 (3H, m,
ArH); dC 8.2 (CH3), 31.1, 40.3 (CH2), 63.7 (CH2OH), 75.1
(COH), 126.3, 127.1, 127.4, 128.9, 129.5, 132.6, 135.2, 140.0,
140.7, 141.1 (ArC); m/z 266 [(MþꢀH2O), 2%], 237 (10), 181
(18), 180 (100), 165 (10); HRMS: MþꢀH2O, found:
266.1675, C19H22O requires: 266.1671.
4.7.4. 1-{[3-(Hydroxymethyl)biphenyl-2-yl]methyl}-
cyclohexanol (17d)
White solid; mp 109e110 ꢁC (hexane/dichloromethane);
Rf¼0.23 (hexane/ethyl acetate 2:1); n (KBr) 3334 (OH),
1257 cmꢀ1 (CO); dH 0.96e1.09 (2H, m, CH2), 1.54e1.64
(8H, m, 4ꢂCH2), 2.87 (2H, br s, 2ꢂOH), 3.13e3.23 (2H, m,
CH2), 4.70 (2H, s, CH2OH), 7.19e7.20 (1H, m, ArH),
7.21e7.46 (7H, m, ArH); dC 21.9, 22.1, 22.2, 25.4, 25.7, 31.7
(CH2), 64.1 (CH2OH), 72.5 (COH), 126.6, 126.7, 126.8,
128.2, 128.4, 130.2, 130.4, 130.9, 133.6, 141.9, 143.2, 144.2
(ArC); m/z 278 (MþꢀH2O, 2%), 181 (17), 180 (100), 179
(20), 178 (14), 166 (12), 165 (54), 81 (10); HRMS: MþꢀH2O,
found: 278.1669; C20H22O requires: 278.1671.
4.8. Cyclisation of diols 18c and 18d. Isolation
of phenylisochromans 19c and 19d: general procedure
Reaction conditions were exactly the same as described in
Section 4.7 for compounds 10. Yields are given in Chart 5;
physical, analytical and spectroscopic data are as follows.
4.7.5. 3-Hydroxymethyl-4-methylbiphenyl (18a)23
Brown oil; Rf¼0.09(hexane/ethyl acetate 10:1); n (film) 3391
(OH), 3056, 3027 cmꢀ1 (ArH); dH 2.05 (1H, br s, OH), 2.42 (3H,
s, CH3), 4.79 (2H, s, CH2OH), 7.27 (1H, d, J¼5.4 Hz, ArH), 7.36
(1H, t, J¼9.3 Hz, ArH), 7.47 (2H, t, J¼10.5 Hz, ArH), 7.63 (2H,
d, J¼9.8 Hz, ArH); dC 18.5 (CH3), 63.7 (CH2O), 126.4, 126.5,
127.1, 127.2, 128.9, 130.1, 135.3, 139.1, 139.2, 141.0 (ArC);
m/z 198 (Mþ, 62%), 181 (18), 180 (100), 179 (18), 178 (11),
165 (39), 155 (18), 154 (12), 153 (12), 152 (19), 89 (10).
4.8.1. 3,7-Diphenylisochroman (19c)
White solid; mp 105e106 ꢁC (hexane/dichloromethane);
Rf¼0.25 (hexane/ethyl acetate 30:1); n (KBr) 3088, 3069,
2033 (ArH), 1092 cmꢀ1 (COC); dH 2.99e3.11 (2H, m,
CH2CH), 4.76 (1H, dd, J¼6.7, 3.8 Hz, CHO), 5.07 (2H, s,
CH2O), 7.20e7.48 (11H, m, ArH), 7.58 (2H, d, J¼9.2 Hz,
ArH); dC 36.0 (CH2), 69.0 (CH2O), 77.1 (CHO), 123.0,
125.5, 126.1, 127.2, 127.4, 128.7, 128.9, 129.4, 132.8,