N. Kise et al. / Tetrahedron 63 (2007) 5415–5426
5421
J¼7.3 Hz), 2.11–2.21 (m, 1H), 2.29 (br s, 1H), 3.62–3.66 (m,
1H), 7.22–7.39 (m, 5H). 13C NMR (CDCl3) d 7.3 (q), 15.3 (q),
22.1 (q), 29.0 (d), 33.4 (t), 79.9 (s), 81.1 (d), 125.4 (d), 126.4
(d), 128.0 (d), 143.0 (s). Anal. Calcd for C13H20O2: C,
74.96%; H, 9.68%. Found: C, 74.94%; H, 9.67%.
paste. Rf 0.35 (hexanes/ethyl acetate¼2:1, silica gel). IR
(neat) 3337, 1601, 1508, 835, 818 cmꢁ1. 1H NMR (CDCl3)
d 0.82 (t, 1.5H, J¼7.3 Hz), 0.85 (t, 1.5H, J¼7.3 Hz), 1.11–
1.50 (m, 6H), 1.51 (s, 1.5H), 1.58 (s, 1.5H), 2.01 (br s,
0.5H), 2.15 (br s, 0.5H), 2.57 (br s, 0.5H), 2.69 (br s, 0.5H),
3.59–3.64 (m, 0.5H), 3.64–3.69 (m, 0.5H), 7.00–7.06 (m,
2H), 7.35–7.39 (m, 1H), 7.41–7.46 (m, 1H). 13C NMR
(CDCl3) d 13.85 (q), 13.86 (q), 22.4 (t), 22.5 (t), 26.81 (q),
26.84 (q), 28.5 (t), 28.6 (t), 30.2 (t), 30.8 (t), 76.3 (s), 76.5
(s), 78.3 (d), 78.5 (d), 114.7 (d, JCCF¼21.1 Hz), 114.8 (d,
4.3.6. 2,5-Dimethyl-3-phenylhexane-3,4-diol (2h). Com-
pound 2h: less polar isomer. White solid, Rf 0.5 (hexanes/
ethyl acetate¼5:1). Mp 55–56 ꢂC. 1H NMR (CDCl3)
d 0.76 (d, 3H, J¼7.1 Hz), 0.83 (d, 3H, J¼6.7 Hz), 0.84 (d,
3H, J¼6.7 Hz), 1.06 (d, 3H, J¼6.9 Hz), 1.32 (d, 1H,
J¼5.1 Hz), 1.99–2.08 (m, 1H), 2.31–2.38 (m, 2H), 3.99
(dd, 1H, J¼2.8, 5.1 Hz), 7.23–7.53 (m, 5H). 13C NMR
(CDCl3) d 16.3 (q), 16.9 (q), 17.2 (q), 22.4 (q), 28.1 (d),
33.6 (d), 77.8 (d), 81.0 (s), 126.5 (d), 126.6 (d), 127.5 (d),
142.8 (s). Anal. Calcd for C14H22O2: C, 75.63%; H,
9.97%. Found: C, 75.56%; H, 9.95%.
JCCF¼21.1 Hz), 127.1 (d, JCCCF¼7.7 Hz), 127.5 (d, JCCCF
7.7 Hz), 140.6 (s, JCCCCF¼2.9 Hz), 141.4 (s, JCCCCF
¼
¼
2.9 Hz), 161.7 (s, JCF¼245.7 Hz), 161.8 (s, JCF¼245.7 Hz).
Anal. Calcd for C13H19FO2: C, 69.00%; H, 8.46%. Found:
C, 68.77%; H, 8.31%.
4.3.11. 2-(4-Fluorophenyl)-4-methylpentane-2,3-diol
(2m). Compound 2m: 50:50 mixture of two diastereomers.
1
4.3.7. 2,5-Dimethyl-3-phenylhexane-3,4-diol (2h). Com-
pound 2h: more polar isomer. White solid. Rf 0.45 (hex-
White solid. Rf 0.5 (hexanes/ethyl acetate¼2:1). H NMR
(CDCl3) d 0.77 (d, 1.5H, J¼7.1 Hz), 0.84 (d, 1.5H, J¼
7.0 Hz), 0.89 (d, 1.5H, J¼6.6 Hz), 0.98 (d, 1.5H, J¼6.8 Hz),
1.44–1.51 (m, 0.5H), 1.54 (s, 1.5H), 1.60 (s, 1.5H), 1.87 (br
d, 0.5H, J¼4.7 Hz), 1.92–1.99 (m, 0.5H), 2.06 (br d, 0.5H,
J¼7.1 Hz), 2.38 (br s, 0.5H), 2.71 (br s, 0.5H), 3.56 (dd,
0.5H, J¼2.7, 6.9 Hz), 3.62 (t, 0.5H, J¼3.8 Hz), 7.00–7.06
(m, 2H), 7.37–7.46 (m, 2H). 13C NMR (CDCl3) d 15.5 (q),
16.5 (q), 22.07 (q), 22.09 (q), 24.2 (q), 28.7 (d), 28.8 (d),
29.2 (q), 76.5 (s), 76.9 (s), 81.2 (d), 81.6 (d), 114.74
(d, JCCF¼21.1 Hz), 114.75 (d, JCCF¼21.1 Hz), 126.6
(d, JCCCF¼7.7 Hz), 127.2 (d, JCCCF¼7.7 Hz), 141.1 (s,
JCCCCF¼2.9 Hz), 142.8 (s, JCCCCF¼2.9 Hz), 161.5 (s,
JCF¼244.2 Hz), 161.7 (s, JCF¼245.2 Hz). Anal. Calcd for
C12H17FO2: C, 67.90%; H, 8.07%. Found: C, 68.07%; H,
8.16%.
1
anes/ethyl acetate¼5:1). Mp 75–77 ꢂC. H NMR (CDCl3)
d 0.71 (d, 3H, J¼6.8 Hz), 0.83 (d, 3H, J¼6.8 Hz), 0.84 (d,
3H, J¼6.8 Hz), 0.90 (d, 3H, J¼7.1 Hz), 1.56–1.65 (m,
1H), 1.86 (d, 1H, J¼7.3 Hz), 2.26–2.35 (m, 1H), 2.37 (br
s, 1H), 4.00 (dd, 1H, J¼2.4, 7.3 Hz), 7.22–7.36 (m, 5H).
13C NMR (CDCl3) d 15.6 (q), 16.9 (q), 18.2 (q), 22.3 (q),
29.2 (d), 36.2 (d), 77.4 (d), 81.3 (s), 126.2 (d), 126.4 (d),
127.5 (d), 141.8 (s). Anal. Calcd for C14H22O2: C,
75.63%; H, 9.97%. Found: C, 75.60%; H, 9.93%.
4.3.8. 2-(4-Methoxyphenyl)heptane-2,3-diol (2i). Com-
pound 2i: 50:50 mixture of two diastereomers. Colorless
paste. Rf 0.35 (hexanes/ethyl acetate¼2:1, silica gel). IR
(neat) 3379, 1612, 1512, 829 cmꢁ1 1H NMR (CDCl3)
.
d 0.82 (t, 1.5H, J¼7.3 Hz), 0.83 (t, 1.5H, J¼7.3 Hz), 1.09–
1.52 (m, 6H), 1.49 (s, 1.5H), 1.55 (s, 1.5H), 2.92 (br s, 2H),
3.57–3.60 (m, 1H), 3.64–3.68 (m, 1H), 3.79 (s, 3H), 6.84–
6.89 (m, 2H), 7.28–7.33 (m, 1H), 7.34–7.39 (m, 1H). 13C
NMR (CDCl3) d 13.81 (q), 13.84 (q), 22.38 (t), 22.43 (t),
26.5 (q), 28.5 (t), 28.7 (t), 30.2 (t), 30.7 (t), 55.0 (q), 76.2
(s), 76.4 (s), 78.4 (d), 78.5 (d), 113.2 (d), 113.3 (d), 126.5 (d),
126.9 (d), 137.0 (s), 137.6 (s), 158.1 (s), 158.4 (s). Anal.
Calcd for C14H22O3: C, 70.56%; H, 9.30%. Found: C,
70.32%; H, 9.37%.
4.3.12. 2-(4-Fluorophenyl)-3-methylbutane-2,3-diol (2n).
White solid. Rf 0.35 (hexanes/ethyl acetate¼2:1, silica
gel). Mp 63–64 ꢂC. IR (KBr) 3412, 1603, 1508, 922, 839,
1
827 cmꢁ1. H NMR (CDCl3) d 1.06 (s, 3H), 1.25 (s, 3H),
1.62 (s, 3H), 2.11 (br s, 1H), 2.76 (br s, 1H), 6.97–7.03 (m,
2H), 7.43–7.49 (m, 2H). 13C NMR (CDCl3) d 24.2 (q),
24.7 (q), 25.0 (q), 75.2 (s), 78.1 (s), 114.1 (d, JCCF¼21.1 Hz),
128.4 (d, JCCCF¼7.7 Hz), 140.4 (s, JCCCCF¼2.9 Hz), 161.7
(s, JCF¼243.8 Hz). Anal. Calcd for C11H15FO2: C,
66.65%; H, 7.63%. Found: C, 66.68%; H, 7.56%.
4.3.9. 2-(4-Methoxyphenyl)-4-methylpentane-2,3-diol
(2j). Compound 2j: 50:50 mixture of two diastereomers.
Colorless paste. Rf 0.5 (hexanes/ethyl acetate¼2:1). 1H
NMR (CDCl3) d 0.77 (d, 1.5H, J¼6.8 Hz), 0.85 (d, 1.5H, J¼
6.9 Hz), 0.87 (d, 1.5H, J¼6.8 Hz), 0.98 (d, 1.5H, J¼6.9 Hz),
1.47–1.55 (m, 0.5H), 1.54 (s, 1.5H), 1.60 (s, 1.5H), 1.89 (br
s, 0.5H), 1.90–197 (m, 0.5H), 2.02 (br s, 0.5H), 2.27 (br s,
0.5H), 2.60 (br s, 0.5H), 3.54 (br s, 0.5H), 3.62 (br d, 0.5H,
J¼2.3 Hz), 3.81 (s, 3H), 6.86–6.90 (m, 2H), 7.32–7.36 (m,
1H), 7.36–7.40 (m, 1H). 13C NMR (CDCl3) d 15.6 (q),
16.7 (q), 22.10 (q), 22.12 (q), 23.9 (q), 28.65 (d), 28.73 (d),
29.0 (q), 55.02 (d), 55.05 (d), 76.5 (s), 76.8 (s), 81.3 (d), 81.6
(d), 113.29 (d), 113.32 (d), 126.0 (d), 126.6 (d), 137.6 (s),
139.0 (s), 158.1 (s), 158.3 (s). Anal. Calcd for C13H20O3:
C, 69.61%; H, 8.99%. Found: C, 69.78%; H, 9.05%.
4.3.13. 4-Methyl-1-(naphthalen-2-yl)pentane-2,3-diol
(2o). Compound 2o: 70:30 mixture of two diastereomers.
Colorless paste. Rf 0.5 (hexanes/ethyl acetate¼2:1). 1H
NMR (CDCl3) d 0.74 (d, 0.9H, J¼6.8 Hz), 0.779 (d, 2.1H,
J¼6.9 Hz), 0.784 (d, 2.1H, J¼6.7 Hz), 1.04 (d, 0.9H,
J¼6.6 Hz), 1.22–1.27 (m, 0.3H), 1.35–1.42 (m, 0.7H),
1.84 (s, 0.9H), 1.85 (s, 2.1H), 2.30 (br s, 0.7H), 2.84 (br s,
0.7H), 2.84 (br s, 0.7H), 3.33 (br s, 0.3H), 4.35 (dd, 0.7H,
J¼2.4, 7.3 Hz), 4.38 (t, 0.3H, J¼4.1 Hz), 7.40–7.50 (m,
3H), 7.72–7.79 (m, 1.3H), 7.84–7.89 (m, 1H), 7.96–7.99
(m, 0.7H), 8.13 (br d, 0.7H, J¼8.3 Hz), 8.51 (br d, 0.3H,
J¼8.3 Hz). 13C NMR (CDCl3) d 15.3 (q), 17.4 (q), 21.7
(q), 21.8 (q), 24.1 (q), 28.8 (q), 29.1 (d), 29.4 (d), 78.2 (s),
78.3 (s), 79.0 (d), 79.1 (d), 123.9 (d), 124.6 (d), 124.7 (d),
124.9 (d), 125.0 (d), 125.1 (d), 125.3 (d), 126.4 (d), 128.0
(d), 128.6 (d), 129.1 (d), 129.3 (d), 130.1 (s), 130.7 (s),
134.4 (s), 134.8 (s), 141.6 (s), 141.7 (s). Anal. Calcd for
4.3.10. 2-(4-Fluorophenyl)heptane-2,3-diol (2l). Com-
pound 2l: 50:50 mixture of two diastereomers. Colorless