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Can. J. Chem. Vol. 00, 0000
calcd for C18H21NNaO4 [M + Na]+ 338.1369, found [M + Na]+
338.1395.
7.4 Hz, 3H); 13C NMR (126 MHz, CDCl3) ␦ 159.7, 158.8, 158.6, 158.1,
156.1, 154.1, 149.0, 132.0, 131.8, 129.60, 129.57, 129.0, 128.3, 127.8,
124.4, 121.0, 119.6, 114.4, 114.2, 114.2, 107.2, 106.5, 106.4, 102.9, 102.8,
99.9, 93.6, 92.66, 92.64, 55.7, 55.38, 55.36, 55.3, 48.0, 47.9, 31.7,
30.2, 29.8, 26.7, 26.3, 14.3, 10.59, 10.54; IR (neat) 3428, 2924, 2918,
1637, 1611, 1559, 1495, 1457, 1374, 1305, 1157, 1117, 1033 cm−1; HRMS
(ESI) calcd for C18H22NO5 [M + H]+ 332.1498, found [M + H]+
332.1425.
( )-2-((1R,2S)-1-(4-Methoxyphenyl)-2-nitrobutyl)-
5-methylphenol (25d)
Following the general protocol for the acid catalyzed nucleo-
philic substitution of benzylic alcohols, starting with 40 mg of
alcohol 3a, using m-cresol as the nucleophile and AuCl3 as the
catalyst, diaryl 25d (42 mg, 71%, dr 20:1) was obtained after 5 h as
a colorless oil. 1H NMR (500 MHz, CDCl3) ␦ 7.35 (d, J = 8.4 Hz, 1H),
7.17 (d, J = 8.6 Hz, 2H), 6.83 (d, J = 8.6 Hz, 2H), 6.63 (dd, J = 8.4, 2.4 Hz,
1H), 6.55 (d, J = 2.3 Hz, 1H), 5.14 (td, J = 11.0, 3.0 Hz, 1H), 4.56 (d, J =
11.4 Hz, 1H), 3.76 (s, 2.9H), 3.73 (s, 0.1H), 2.32 (s, 0.1H), 2.25 (s, 2.9H),
1.87 (ddq, J = 14.5, 10.5, 7.3 Hz, 1H), 1.69 (dqd, J = 14.8, 7.4, 3.1 Hz, 1H),
0.92 (t, J = 7.4 Hz, 3H); 13C NMR (126 MHz, CDCl3) ␦ 158.8, 154.5,
138.2, 131.1, 130.7, 129.7, 126.3, 118.1, 114.5, 113.1, 93.4, 55.4, 49.3,
26.8, 19.9, 10.5; IR (neat) 3405, 2975, 2944, 2861, 1635, 1540, 1456,
1249, 1216, 1136, 1033 cm−1; HRMS (ESI) calcd for C18H25N2O4 [M +
NH4]+ 333.1809, found [M + NH4]+ 333.1783 and calcd for
C18H21NNaO4 [M + Na]+ 338.13628, found [M + Na]+ 338.13654.
( )-2-((1R,2S)-2-Azido-1-(4-methoxyphenyl)propyl)-
4,6-dimethylphenol (25h)
Following the general protocol for the acid catalyzed nucleo-
philic substitution of benzylic alcohols, starting with 50 mg of
alcohol15a,using2,4-dimethylphenolasthenucleophileandp-tol-
uenesulfonic acid monohydrate as the catalyst, diaryl 25h (43 mg,
58%, dr 6:1) was obtained overnight as a colorless oil. Rf = 0.12
(hexane/ethyl acetate 9:1); 1H NMR (500 MHz, CDCl3) ␦ 7.31–7.27 (m,
0.33H), 7.23–7.17 (m, 1.67H), 6.90 (d, J = 1.6 Hz, 0.85H), 6.88–6.80 (m,
3.15H), 5.25 (s, 0.8H), 4.35–4.26 (m, 1H), 4.18 (d, J = 8.8 Hz, 0.15H),
4.12 (d, J = 9.1 Hz, 0.85H), 3.78 (s, 0.5H), 3.78 (s, 2.5H), 2.25 (s, 2.5H),
2.23 (s, 0.5H), 2.19 (s, 2.5H), 2.17 (s, 0.5H), 1.32–1.28 (m, J = 9.5, 6.4 Hz,
3H); 13C NMR (126 MHz, CDCl3) ␦ 158.5, 149.9, 133.1, 130.3, 123.0,
129.8, 129.6, 129.5, 127.6, 127.4, 127.1, 124.6, 114.2, 114.1, 60.7, 60.2,
55.3, 51.1, 50.3, 20.9, 18.8, 18.6, 16.3, 16.1; IR (neat) 3423, 2925, 2100,
1685, 1607, 1582, 1509, 1482, 1454, 1377, 1301, 1245, 1178, 1123,
1033 cm−1; HRMS (ESI) calcd for C18H21N3NaO2 [M + Na]+ 334.1532,
found [M + Na]+ 334.1689.
( )-2,6-Dimethoxy-3-((1R,2S)-1-(4-methoxyphenyl)-
2-nitrobutyl)phenol (25e)
Following the general protocol for the acid catalyzed nucleo-
philic substitution of benzylic alcohols, starting with 50 mg of
alcohol 3a, using 2,6-dimethoxyphenol as the nucleophile and
AuCl3 as the catalyst, diaryl 25e (51 mg, 64%, dr 20:1) was obtained
overnight as a white oil. Rf = 0.16 (hexane/ethyl acetate 8:2);
1H NMR (400 MHz, CDCl3) ␦ 7.25–7.18 (m, 2H), 6.92 (d, J = 8.6 Hz,
1H), 6.85–6.77 (m, 2H), 6.60 (d, J = 8.6 Hz, 1H), 5.45 (s, 0.8H), 5.19
(ddd, J = 11.7, 10.6, 3.1 Hz, 1H), 4.79 (d, J = 11.8 Hz, 1H), 3.83 (s, 3H),
3.80 (s, 3H), 3.75 (s, 3H), 1.89 (ddq, J = 14.5, 10.4, 7.2 Hz, 1H), 1.73
(dqd, J = 14.9, 7.5, 3.2 Hz, 1H), 0.93 (t, J = 7.4 Hz, 3H); 13C NMR
(126 MHz, CDCl3) ␦ 158.8, 147.1, 145.0, 139.0, 131.9, 129.6, 126.8,
116.3, 114.4, 106.2, 92.8, 60.5, 56.2, 55.4, 47.3, 26.7, 10.6; IR (neat)
3491, 2936, 2838, 1609, 1548, 1511, 1496, 1319, 1247, 1088 cm−1;
HRMS (ESI) calcd for C19H24NO6 [M + H]+ 362.15981, found [M + H]+
362.16152 and calcd for C19H27N2O6 [M + NH4]+ 379.18636, found
[M + NH4]+ 379.18629.
( )-2-((1R,2S)-2-Azido-1-(4-methoxyphenyl)-3-methylbutyl)-
4-methylphenol (25i)
Following the general protocol for the acid catalyzed nucleo-
philic substitution of benzylic alcohols, starting with 50 mg of
alcohol 15b, using p-cresol as the nucleophile and p-toluenesul-
fonic acid monohydrate as the catalyst, diaryl 25i (52 mg, 76%, dr
7:1) was obtained overnight as a white solid. mp: 112–113 °C;
1H NMR (500 MHz, CDCl3) ␦ 7.42–7.37 (m, 3H), 7.26–7.22 (m, 1.7H),
7.09 (d, J = 1.8 Hz, 0.85H), 7.01 (d, J = 1.9 Hz, 0.15H), 6.91 (dd, J = 8.1,
2.1 Hz, 0.85H), 6.87–6.83 (m, 2.15H), 6.70 (d, J = 8.1 Hz, 0.85H), 6.58
(d, J = 8.1 Hz, 0.15H), 5.66 (s, 0.6H), 4.37 (dd, J = 9.7, 4.0 Hz, 1H), 4.09
(dd, J = 9.9, 3.7 Hz, 0.15H), 3.98 (dd, J = 9.4, 4.6 Hz, 0.85H), 3.78 (s,
0.5H), 3.78 (s, 2.5H), 2.27 (s, 2.5H), 2.26 (s, 0.5H), 1.89–1.83 (m,
0.15H), 1.83–1.72 (m, 0.85H), 1.08–1.02 (m, 3H), 0.98 (d, J = 6.7 Hz,
2.5H), 0.91 (d, J = 6.7 Hz, 0.5H); 13C NMR (126 MHz, CDCl3) ␦ 158.5,
151.5, 150.6, 133.9, 133.2, 130.4, 130.3, 129.9, 129.7, 129.5, 128.7,
128.5, 128.2, 127.6, 116.9, 116.0, 114.3, 114.1, 73.0, 72.0, 66.0, 55.4,
48.1, 47.5, 30.9, 30.7, 29.8, 21.3, 21.1, 20.9, 16.6, 16.0, 15.4; IR (neat)
3402, 2963, 2930, 2873, 2096, 1670, 1573, 1541, 1462, 1482, 1454,
1357, 1388, 1225, 1141, 1135, 1028 cm−1; HRMS (ESI) calcd for
C19H23N3NaO2 [M + Na]+ 348.1688, found [M + Na]+ 348.1651.
( )-2-Methoxy-5-((1R,2S)-1-(4-methoxyphenyl)-
2-nitrobutyl)phenol (25f)
Following the general protocol for the acid catalyzed nucleo-
philic substitution of benzylic alcohols, starting with 30 mg of
alcohol 3a, using 2-methoxyphenol as the nucleophile and AuCl3
as the catalyst, diaryl 25f (37 mg, 84%, dr 4:1) was obtained after 5 h
1
as a colorless oil. H NMR (500 MHz, CDCl3) ␦ 7.19–7.16 (m, 2H),
6.88–6.73 (m, 5H), 5.56 (s, 0.25H), 5.51 (s, 0.75H), 5.15–5.07 (m, 1H),
4.29 (dd, J = 16.4, 8.0 Hz, 1H), 3.84 (s, 2.4H), 3.81 (s, 0.6H), 3.77 (s,
2.4H), 3.76 (s, 0.6H), 1.94–1.81 (m, 1H), 1.72 (dqd, J = 14.9, 7.5, 3.0 Hz,
1H), 0.95–0.90 (m, J = 7.4, 2.8 Hz, 3H); 13C NMR (126 MHz, CDCl3) ␦
158.9, 158.9, 146.7, 145.88, 145.85, 145.0, 133.5, 132.2, 132.04, 131.98,
129.1, 128.5, 119.9, 118.9, 114.8, 114.6, 114.4, 113.8, 110.9, 110.4, 93.9,
93.8, 56.02, 55.97, 55.4, 54.5, 54.3, 26.6, 26.5, 10.5; IR (neat) 3421,
2929, 2905, 1618, 1571, 1499, 1456, 1417, 1314, 1129, 1102, 1031 cm−1;
HRMS (ESI) calcd for C18H22NO5 [M + H]+ 332.1498, found [M + H]+
332.1466.
( )-2-((1R,2S)-2-Azido-1-(4-methoxyphenyl)-3-methylbutyl)-
4-methoxyphenol (25j)
Following the general protocol for the acid catalyzed nucleo-
philic substitution of benzylic alcohols, starting with 50 mg of
alcohol 15b, using 4-methoxyphenol as the nucleophile and
p-toluenesulfonic acid monohydrate as the catalyst, diaryl 25j
(60 mg, 84%, dr 5:1) was obtained overnight as a colorless oil. 1H NMR
(500 MHz, CDCl3) ␦ 7.41–7.38 (m, 0.33H), 7.24 (dd, J = 6.8, 5.0 Hz,
1.67H), 6.90 (d, J = 2.7 Hz, 0.8H), 6.87–6.83 (m, 2H), 6.80 (d, J = 2.4 Hz,
0.2H), 6.75 (s, 0.3H), 6.73 (s, 0.5H), 6.67 (d, J = 3.0 Hz, 0.5H), 6.66 (d,
J = 3.0 Hz, 0.3H), 5.59 (s, 0.8H), 4.40 (d, J = 9.7 Hz, 1H), 4.05 (dd, J =
9.7, 3.8 Hz, 0.2H), 3.97 (dd, J = 9.6, 4.1 Hz, 0.8H), 3.77 (s, 2.5H), 3.76
(s, 0.5H), 3.75 (s, 2.5H), 3.74 (s, 0.5H), 1.91–1.76 (m, 1H), 1.07–1.03 (m,
3H), 0.97 (d, J = 6.7 Hz, 2.5H), 0.93 (d, J = 6.7 Hz, 0.5H); 13C NMR
(126 MHz, CDCl3) ␦ 158.5, 153.9, 147.7, 147.0, 133.5, 132.9, 130.0,
129.9, 129.5, 129.5, 117.7, 116.6, 116.2, 115.6, 115.0, 114.3, 114.1, 112.7,
111.9, 73.1, 72.0, 66.0, 56.2, 55.3, 47.5, 47.3, 30.9, 30.7, 21.3, 21.1, 16.3,
16.1, 15.3; IR (neat) 3418, 2895, 2807, 2102, 1673, 1640, 1587, 1499,
( )-5-Methoxy-2-((1R,2S)-1-(4-methoxyphenyl)-
2-nitrobutyl)phenol (25g)
Following the general protocol for the acid catalyzed nucleo-
philic substitution of benzylic alcohols, starting with 30 mg of
alcohol 3a, using 3-methoxyphenol as the nucleophile and AuCl3
as the catalyst, diaryl 25g (37 mg, 76%, dr 20:1) was obtained after
5 h as a colorless oil. 1H NMR (500 MHz, CDCl3) ␦ 7.28–7.17 (m, 3H),
6.85–6.76 (m, 2H), 6.46–6.21 (m, 2H), 5.30 (ddd, J = 24.7, 12.4, 2.7 Hz,
1H), 4.70 (dd, J = 11.6, 3.5 Hz, 1H), 3.76 (s, 3H), 3.73 (s, 1.5H), 3.67 (s,
1.5H), 1.87 (dtt, J = 21.4, 14.5, 7.3 Hz, 1H), 1.78–1.65 (m, 1H), 0.92 (q, J =
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