M. Bossart, R. Fässler, J. Schoenberger, A. Studer
FULL PAPER
4-[5-(Dimethylamino)-1-naphthyl]-2-pentanol (6h): This compound
was obtained by GP 1, from sulfonate 5h (165 mg, 0.37 mmol),
benzene (12 mL), Bu3SnH (147 µL, 0.55 mmol), AIBN (18 mg,
C6H11); 1.43Ϫ1.90 (m, 6 H, C6H11); 1.64 (d, J ϭ 6.7 Hz, 3 H, CH3);
1.92Ϫ2.07 (m, 2 H, CH2); 3.86Ϫ3.94 (m, 1 H, HCBr); 4.76Ϫ4.79
(m, 1 H, HCO); 7.54Ϫ7.59 (m, 2 aromat. H); 7.64Ϫ7.68 (m, 1
0.11 mmol) in benzene (0.5 mL), and MeLi (1.7 mL, 1.1 mmol). aromat. H); 7.92Ϫ7.98 (m, 2 aromat. H); isomer B: 0.88Ϫ1.26 (m,
Purification by FC (ether/pentane, 1:2) afforded 6h (49 mg, 52%).
5 H, C6H11); 1.43Ϫ1.90 (m, 6 H, C6H11); 1.65 (d, J ϭ 6.6 Hz, 3 H,
CH3); 1.92Ϫ2.07 (m, 1 H, CH2); 2.21Ϫ2.28 (m, 1 H, CH2);
The diastereoisomer ratio (u/l ϭ 11:1) was determined by 1H NMR
spectroscopy. IR (CHCl3): 3602w, 3444w, 2967s, 2830m, 1592m, 3.97Ϫ4.05 (m, 1 H, HCBr); 4.56Ϫ4.60 (m, 1 H, HCO); 7.54Ϫ7.59
1510m, 1455m, 1404s, 1306m, 1139m, 1049w, 1003w, 959m, 840w. (m, 2 aromat. H); 7.64Ϫ7.68 (m, 1 aromat. H); 7.92Ϫ7.98 (m, 2
1H NMR (400 MHz): 1.17 (d, J ϭ 6.2 Hz, 3 H, CH3); 1.38 (d, J ϭ aromat. H) ppm. 13C NMR (100 MHz): isomer A: 25.9 (CH2); 26.1
7.0 Hz, 3 H, CH3); 1.87Ϫ1.95 (m, 2 H, CH2); 3.22 [s, 6 H,
N(CH3)2]; 3.60Ϫ3.70 (m, 1 H, CHAryl); 4.10Ϫ4.20 (m, 1 H, CHO);
(CH2); 26.3 (CH2); 26.9 (CH3); 27.2 (CH2); 28.3 (CH2); 42.2 (CH);
42.5 (CH2); 47.4 (CH); 86.9 (CH); 127.8 (CH); 129.2 (CH); 133.6
7.21 (d, J ϭ 6.7 Hz, 1 aromat. H); 7.57Ϫ7.64 (m, 2 aromat. H); (CH); 137.4 (C); isomer B: 25.8 (CH3); 25.9 (CH2); 26.0 (CH2);
8.32Ϫ8.39 (m, 2 aromat. H); 8.61 (d, J ϭ 8.4 Hz, 1 aromat. H) 26.1 (CH2); 27.1 (CH2); 28.3 (CH2); 40.6 (CH); 42.2 (CH2); 45.2
ppm. 13C NMR (100 MHz): 23.1 (CH3); 24.1 (CH3); 30.7 (CH);
(CH); 85.7 (CH); 127.7 (CH); 129.2 (CH); 133.7 (CH); 137.3 (C)
44.2 (CH3); 47.5 (CH2); 66.2 (CH); 115.2 (CH); 118.3 (CH); 122.7 ppm. EI-MS: 293.0 (29) [M Ϫ C6H11]ϩ, 253.1 (14), 218.1 (51),
(CH); 123.5 (CH); 128.8 (CH); 131.4 (C); 132.2 (C); 143.5 (C); 141.0 (100), 109.1 (20), 95.1 (92), 77.1 (64), 55.1 (28). C16H23BrO3S
152.4 (C) ppm. EI-MS: 257.1 (100, [M]ϩ), 239.1 (10), 212.1 (12), (375.33): calcd. C 51.20, H 6.18; found C 51.42, H 6.05.
199.1 (88), 168.1 (22), 183.1 (22), 168.0 (13), 153.0 (21). HRMS:
C17H23NO [M]ϩ: calcd. 257.1774; found 257.1779.
3-Bromo-1-isopropylbutyl Benzenesulfonate (7b): 5-Bromo-2-
methyl-3-hexanol (574 mg, 2.94 mmol, see Supporting Informa-
tion) was treated according to a procedure reported by Tipson[13]
with pyridine (15 mL) and benzenesulfonyl chloride (1.5 mL,
11.7 mmol). After workup, unchanged sulfonyl chloride was re-
moved by stirring the crude product with imidazole (400 mg,
5.9 mmol) in CH2Cl2 (10 mL) for 1 h at room temp. After purifica-
tion by FC (ether/pentane, 1:4), 7b (740 mg, 75%) was obtained.
IR (CHCl3): 3566w, 3011m, 2970s, 1467m, 1448s, 1363s, 1175s,
1096s, 952m, 895s, 827m, 605s. 1H NMR (400 MHz): isomer A:
0.88 (d, J ϭ 6.9 Hz, 6 H, CH3); 1.66 (d, J ϭ 6.7 Hz, 3 H, CH3);
1.85Ϫ2.09 (m, 3 H); 3.89Ϫ3.99 (m, 1 H, HCBr); 4.77Ϫ4.81 (m, 1
H, HCO); 7.52Ϫ7.59 (m, 2 aromat. H); 7.64Ϫ7.68 (m, 1 aromat.
H); 7.90Ϫ7.97 (m, 2 aromat. H); isomer B: 0.88 (d, J ϭ 7.0 Hz, 6
H, CH3); 1.66 (d, J ϭ 6.6 Hz, 3 H, CH3); 1.85Ϫ2.09 (m, 2 H, CH2);
2.22Ϫ2.29 (m, 1 H); 3.99Ϫ4.06 (m, 1 H, HCBr); 4.59Ϫ4.63 (m, 1
H, HCO); 7.52Ϫ7.59 (m, 2 aromat. H); 7.64Ϫ7.68 (m, 1 aromat.
H); 7.90Ϫ7.97 (m, 2 aromat. H) ppm. 13C NMR (100 MHz): iso-
mer A: 16.6 (CH3); 17.8 (CH3); 26.9 (CH3); 32.0 (CH); 41.6 (CH2);
47.4 (CH); 87.0 (CH); 129.2 (CH); 133.7 (CH); 137.3 (C); isomer
B: 16.5 (CH3); 17.8 (CH3); 25.8 (CH3); 30.6 (CH); 42.0 (CH2); 45.1
(CH); 85.9 (CH); 127.7 (CH); 129.2 (CH); 133.7 (CH); 137.2 (C)
ppm. EI-MS: 335.1 (6) [M ϩ H]ϩ, 317.0 (8), 293.0 (28), 291.0 (27),
220.9 (15), 213.0 (19), 178.0 (10), 141.0 (100), 97.1 (54), 78.0 (21),
77.0 (94), 71.0 (51), 56.1 (14).
4-(2-Thienyl)-2-pentanol (6i): This compound was obtained by GP
1, from sulfonate 5i (103 mg, 0.29 mmol), benzene (9 mL), Bu3SnH
(114 µL, 0.43 mmol), AIBN (14 mg, 0.08 mmol) in benzene
(0.5 mL), and MeLi (0.8 mL, 1.3 mmol). Purification by FC (ether/
pentane, 1:3) afforded 6i (36 mg, 74%). The diastereoisomer ratio
(u/l ϭ 9:1) was determined by GC analysis. IR (CHCl3): 3607w,
3451m, 3008s, 2969s, 2928s, 1601w, 1456m, 1379m, 1261w, 1093m,
1038w, 944m, 907w, 848m, 826m. 1H NMR (300 MHz): 1.22 (d, J ϭ
6.2 Hz, 3 H, CH3); 1.35 (d, J ϭ 6.8 Hz, 3 H, CH3); 1.63Ϫ1.75 (m,
1 H, CH2); 1.82Ϫ1.92 (m, 1 H, CH2); 3.23 (sx, J ϭ 7.2 Hz, 1 H,
HCAryl); 3.83Ϫ3.89 (m, 1 H, HCO); 6.82Ϫ6.84 (m, 1 aromat. H);
6.91Ϫ6.94 (m, 1 aromat. H); 7.12Ϫ7.15 (m, 1 aromat. H) ppm. 13
C
NMR (75 MHz): 23.2 (CH3); 23.9 (CH3); 32.5 (CH); 48.9 (CH2);
66.3 (CH); 122.7 (CH); 122.9 (CH); 126.8 (CH); 152.0 (C) ppm.
EI-MS: 170.1 (11) [M]ϩ, 152.1 (29), 137.1 (53), 111.1 (100), 97.0
(16), 77.1 (8). C9H14OS (170.28): calcd. C 63.48, H 8.29; found C
63.46, H 8.43.
4-(3-Pyridyl)-2-pentanol (6j): This compound was obtained by GP
1, from sulfonate 5j (173 mg, 0.49 mmol), benzene (16 mL),
Bu3SnH (233 µL, 0.88 mmol), AIBN (40 mg, 0.25 mmol) in ben-
zene (0.5 mL), and MeLi (1.2 mL, 1.9 mmol). Purification by FC
(MTBE/acetone, 4:1) afforded 6j (30 mg, 37%). The diastereo-
isomer ratio (u/l ϭ 7:1) was determined by GC analysis. IR (nujol):
3353br, 3037w, 2964s, 2927m, 2874w, 1654w, 1459m, 1427s, 1375m,
1131m, 1029m, 809m, 716s. 1H NMR (200 MHz): 1.14 (d, J ϭ
6.2 Hz, 3 H, CH3); 1.21 (d, J ϭ 7.0 Hz, 3 H, CH3); 1.61Ϫ1.74 (m,
2 H, CH2); 2.86 (sx, J ϭ 7.5 Hz, 1 H, CHAryl); 3.74Ϫ3.81 (m, 1
H, HCO); 7.17Ϫ7.25 (m, 1 aromat. H); 7.44Ϫ7.48 (m, 1 aromat.
H); 8.35Ϫ8.40 (m, 2 aromat. H) ppm. 13C NMR (100 MHz): 21.7
(CH3); 24.0 (CH3); 34.1 (CH); 47.4 (CH2); 65.7 (CH); 123.5 (CH);
134.2 (C); 142.0 (C); 147.5 (C); 148.9 (C) ppm. EI-MS: 147.1 (100)
[M Ϫ H2O]ϩ, 106.1 (100). HRMS: C10H13N [M Ϫ H2O]ϩ: calcd.
147.1048; found 147.1056.
3-Bromo-1-tert-butylbutyl Benzenesulfonate (7c): 5-Bromo-2,2-di-
methyl-3-hexanol (544 mg, 2.6 mmol, see Supporting Information)
was treated according to a procedure reported by Tipson[13] with
pyridine (15 mL) and benzenesulfonyl chloride (1.35 mL,
10.3 mmol). After workup, unchanged sulfonyl chloride was re-
moved by stirring the crude product with imidazole (350 mg,
5.2 mmol) in CH2Cl2 (10 mL) for 1 h at room temp. After purifica-
tion by FC (ether/pentane, 1:4), 7c (380 mg, 42%) was obtained.
IR (CHCl3): 3569s, 3032m, 2971s, 2874m, 1673s, 1480s, 1448s,
1400s, 1361s, 1290m, 1262m, 1174s, 1096s, 988m, 928s, 886s, 600s.
1H NMR (400 MHz): isomer A: 0.89 [s, 9 H, C(CH3)3]; 1.66 (d,
J ϭ 6.6 Hz, 3 H, CH3); 1.94Ϫ2.07 (m, 2 H, CH2); 4.06Ϫ4.16 (m, 1
3-Bromo-1-cyclohexylbutyl Benzenesulfonate (7a): 3-Bromo-1-
cyclohexyl-1-butanol (470 mg, 2.0 mmol, see Supporting Informa-
tion) was treated according to a procedure reported by Tipson[13] H, HCBr); 4.78 (dxd, J1 ϭ 8.9 Hz, J2 ϭ 1.4 Hz, 1 H, HCO);
with pyridine (5 mL) and benzenesulfonyl chloride (1.0 mL,
8.0 mmol). After workup, unchanged sulfonyl chloride was re-
moved by stirring the crude product with imidazole (1.0 g,
14.7 mmol) in CH2Cl2 (5 mL) for 1 h at room temp. After purifica-
7.52Ϫ7.58 (m, 3 aromat. H); 7.93Ϫ7.97 (m, 2 aromat. H); isomer
B: 0.90 [s, 9 H, C(CH3)3]; 1.74 (d, J ϭ 6.5 Hz, CH3); 2.06Ϫ2.12 (m,
1 H, CH2); 2.34Ϫ2.41 (m, 1 H, CH2); 4.16Ϫ4.23 (m, 1 H, HCBr);
4.47 (dxd, J1 ϭ 9.7 Hz, J2 ϭ 2.1 Hz, 1 H, HCO); 7.62Ϫ7.68 (m, 3
tion by FC (ether/pentane, 1:4), 7a (500 mg, 80%) was obtained. aromat. H); 7.90Ϫ7.93 (m,
IR (CHCl3): 3035w, 2933s, 2856m, 1588w, 1449s, 1361s, 1174s, (100 MHz): isomer A: 26.1 (CH3); 27.1 (CH3); 35.1 (C); 42.7 (CH2);
1096m, 900s. H NMR (400 MHz): isomer A: 0.88Ϫ1.26 (m, 5 H, 48.1 (CH); 90.9 (CH); 127.6 (CH); 129.0 (CH); 133.5 (CH); 137.7
2
aromat. H) ppm. 13C NMR
1
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Eur. J. Org. Chem. 2002, 2742Ϫ2757