Cadot et al.
1010 cm-1. MS (EI, 70 eV) m/z 148 (M+, 78), 147 (100), 133
(25), 115 (27), 91 (34), 77 (11), 51 (7).
(b) Prepared according to method A from 1 (402 µL, 3 mmol).
Purification by flash chromatography (petroleum ether/ethyl
acetate 80:20) afforded 4 (315 mg, 71%) as a 10:1 mixture of
two isomers (1H NMR).
(c) Prepared according to method A without catechol from
1 (402 µL, 3 mmol). Purification by flash chromatography
(petroleum ether/ethyl acetate 80:20) afforded 4 (288 mg, 65%)
as a 10:1 mixture of two isomers (1H NMR).
µL, 3 mmol). Purification by flash chromatography (petroleum
ether/ethyl acetate 80:20) afforded 12 (383 mg, 71%) as a 11:1
mixture of two isomers. Colorless oil. 12a : 1H NMR (300 MHz,
CDCl3) δ 1.66 (m, 4H), 3.34 (br s, 1H), 3.50 (t, J ) 5.9 Hz,
2H), 3.58 (t, J ) 6.1 Hz, 2H), 4.50 (s, 2H), 7.20-7.38 (m, 5H).
13C NMR (75 MHz, CDCl3) δ 26.2, 29.5, 62.0, 70.0, 72.6, 127.3,
127.4 (2C), 128.1 (2C), 137.9. IR (neat) 3380, 1450, 1365, 1210,
1100, 1060 cm-1. MS (EI, 70 eV) m/z 180 (MH+, 2), 161 (3),
107 (70), 91 (100), 79 (14), 55 (5). Anal. Calcd for C11H16O2
(180.25): C, 73.30; H, 8.95. Found: C, 73.22; H, 9.09. 12b:
1H NMR (300 MHz, CDCl3) δ 1.21 (d, J ) 6.2 Hz, 3H), 1.76
(m, 2H), 2.90 (br s, 1H), 3.69 (m, 2H), 4.02 (m, 1H), 4.55 (s,
2H), 7.34 (m, 5H). 13C NMR (75 MHz, CDCl3/TMS) δ 23.3, 38.1,
67.6, 69.1, 73.3, 127.6 (2C), 127.7, 128.4 (2C), 137.9. IR (neat)
3400, 1495, 1450, 1370, 1205, 1100, 1025 cm-1. MS (EI, 70
eV) m/z 180 (M+, 1), 161 (18), 120 (17), 107 (52), 91 (100), 79
(14), 56 (14). Anal. Calcd for C11H16O2 (180.25): C, 73.30; H,
8.95. Found: C, 73.13; H, 9.07.
(1R*,2S*)-2-P h en ylcycloh exan ol (tr a n s-5) an d (1S*,2S*)-
2-P h en ylcycloh exa n -1-ol (cis-5).48 Prepared according to
method B from 2 (477 µL, 3 mmol). Purification by flash
chromatography (petroleum ether/ethyl acetate 80:20) afforded
5 (338 mg, 64%) as a 9:1 mixture of two isomers. trans-5: Waxy
1
white solid. Mp 54-55 °C. H NMR (300 MHz, CDCl3) δ 1.45
(m, 4H), 1.68 (br s, 1H), 1.78 (m, 1H), 1.88 (m, 2H), 2.12 (m,
1H), 2.44 (td, J ) 12.9 and 3.7 Hz, 1H), 3.65 (td, J ) 10.0 and
4.0 Hz, 1H), 7.27-7.36 (m, 5H). 13C NMR (75 MHz, CDCl3) δ
24.9, 25.9, 33.2, 34.3, 53.1, 74.2, 126.6, 127.8 (2C), 128.6 (2C),
143.3. IR (KBr) 3300, 1490, 1445, 1335, 1305, 1280, 1230, 1200,
1050 cm-1. MS (EI, 70 eV) m/z 176 (M+, 93), 158 (14), 130 (64),
104 (49), 91 (100), 77 (16), 57 (11). cis-5: Waxy white solid.
Mp 46-48 °C. 1H NMR (300 MHz, CDCl3) δ 1.37 (m, 2H), 1.64
(m, 4H), 1.97 (m, 3H), 2.72 (td, J ) 12.9 and 2.9 Hz, 1H), 4.00
(m, 1H), 7.25 (m, 5H). 13C NMR (75 MHz, CDCl3) δ 19.5, 24.3,
26.2, 32.9, 47.9, 70.5, 123.4, 127.7 (2C), 128.4 (2C), 143.9. IR
(KBr) 3430, 1600, 1495, 1450, 1380, 1330, 1280, 1260, 1225,
1180, 1120, 1050 cm-1. MS (EI, 70 eV) m/z 176 (M+, 80), 158
(12), 117 (42), 104 (46), 91 (100), 78 (14), 57 (12).
1-[Meth yl(p-tolu en esu lfon yl)am in o]pr opan ol (13a) an d
1-[Meth yl(p-tolu en esu lfon yl)am in o]pr opan -2-ol (13b). Pre-
pared according to method B from 9 (675 µL, 3 mmol). Flash
chromatography (petroleum ether/ethyl acetate 20:80) gave 13
(590 mg, 81%) as a 2:1 mixture of two isomers. Colorless oil.
13a : 1H NMR (300 MHz, CDCl3) δ 1.72 (m, 2H), 2.39 (s, 3H),
2.69 (br s, 1H), 2.71 (s, 3H), 3.08 (t, J ) 6.6 Hz, 2H), 3.71 (t,
J ) 5.7 Hz, 2H), 7.30 (d, J ) 8.1 Hz, 2H), 7.64 (d, J ) 8.1 Hz,
2H). 13C NMR (75 MHz, CDCl3) δ 21.3, 29.9, 34.8, 46.6, 58.7,
127.1 (2C), 129.6 (2C), 134.1, 143.4. IR (neat) 3460, 1600, 1460,
1335, 1165, 1085, 1050 cm-1. MS (EI, 70 eV) m/z 243 (M+, 1),
198 (97), 155 (100), 91 (93), 65 (15); Anal. Calcd for C11H17NSO3
(243.33): C, 54.30; H, 7.04; N, 5.75. Found: C, 54.17; H, 7.24;
N, 5.63. 13b: 1H NMR (300 MHz, CDCl3) δ 1.16 (d, J ) 6.6
Hz, 3H), 2.39 (s, 3H), 2.78 (s, 3H), 2.79 (m, 2H), 3.00 (dd, J )
13.8 and 8.3 Hz, 1H), 3.96 (m, 1H), 7.30 (d, J ) 8.1 Hz, 2H),
7.64 (d, J ) 8.5 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ 20.2,
21.3, 36.5, 57.5, 63.4, 127.2 (2C), 129.6 (2C), 133.9, 143.5. IR
(neat) 3450, 1460, 1340, 1160, 1085 cm-1. MS (EI, 70 eV) m/z
243 (M+, 1), 198 (82), 155 (100), 91 (80), 65 (15). Anal. Calcd
for C11H17NSO3 (243.33): C, 54.30; H, 7.04; N, 5.75. Found:
C, 54.56; H, 7.46; N, 5.61.
(1R*,2R*)-Cycloh exan e-1,2-diol (tr a n s-6) an d (1R*,2S*)-
Cycloh exa n e-1,2-d iol (cis-6). Prepared according to method
B from 3 (583 µL, 3 mmol). Purification by flash chromatog-
raphy (petroleum ether/ethyl acetate 20:80) afforded 6 (160
mg, 46%) as a 4:1 mixture of two isomers. trans-6: Waxy white
1
solid. Mp 105-107 °C. H NMR (300 MHz, CDCl3) δ 1.48 (m,
4H), 1.89 (m, 2H), 2.15 (m, 2H), 3.48 (m, 2H), 5.06 (br s, 2H).
13C NMR (75 MHz, CDCl3) δ 25.5 (2C), 34.3 (2C), 84.1 (2C).
IR (KBr) 3380, 1445, 1360, 1350, 1290, 1235, 1195, 1065, 1040
cm-1. MS (EI, 70 eV) m/z 116 (M+, 12), 98 (38), 83 (37), 70
(100), 57 (53). cis-6: Waxy white solid. Mp 98-99 °C. 1H NMR
(300 MHz, CDCl3) δ 1.51 (m, 2H), 1.78 (m, 4H), 1.95 (m, 2H),
3.88 (m, 2H), 5.00 (br s, 2H). 13C NMR (75 MHz, CDCl3) δ 23.0
(2C), 31.1 (2C), 72.0 (2C). IR (KBr) 3395, 3275, 2516, 2430,
1440, 1365, 1260, 1130, 1075 cm-1. MS (EI, 70 eV) m/z 116
(M+, 16), 98 (40), 83 (39), 70 (100), 57 (53).
R-[3-(2-H yd r oxyet h yl)-1-a za b icyclo[2.2.2]oct -6-yl]-6-
m eth oxyqu in olein e-4-m eth a n ol (14a ). Prepared according
to method B from 10 (972 mg, 3 mmol). Purification by flash
chromatography (CH2Cl2/methanol 80:20; CH2Cl2/methanol 50:
50) gave 14a (636 mg, 62%) as a single isomer. Waxy white
1
2-P h en yleth a n ol (11a ) a n d 1-P h en yleth a n ol (11b).49
Prepared according to method B from 7 (344 µL, 3 mmol).
Purification by flash chromatography (petroleum ether/ethyl
acetate 80:20) gave 11 (252 mg, 69%) as a 9:1 mixture of two
isomers. Colorless oil. 11a : 1H NMR (300 MHz, CDCl3) δ 2.65
(br s, 1H), 2.88 (t, J ) 6.6 Hz, 2H), 3.85 (t, J ) 6.2 Hz, 2H),
7.22-7.37 (m, 5H). 13C NMR (75 MHz, CDCl3) δ 38.9, 63.3,
126.2, 128.3 (2C), 128.8 (2C), 138.5. IR (neat) 3440, 1600, 1490,
1450, 1180, 1045 cm-1. MS (EI, 70 eV) m/z 122 (M+, 35), 103
(4), 91 (100), 77 (5), 65 (15), 51 (5). 11b: 1H NMR (300 MHz,
CDCl3) δ 1.48 (d, J ) 6.6 Hz, 3H), 2.90 (br s, 1H), 4.85 (q, J )
6.6 Hz, 1H), 7.31 (m, 1H), 7.38 (m, 4H). 13C NMR (75 MHz,
CDCl3) δ 24.9, 70.0, 125.3 (2C), 127.2, 128.2 (2C), 145.7. IR
(neat) 3350, 1600, 1490, 1450, 1370, 1200, 1075, 1030, 1010
cm-1. MS (EI, 70 eV) m/z 122 (M+, 39), 107 (100), 79 (84), 51
(15).
solid. Mp 201-202 °C; [R]D -150° (c 1, MeOH). H NMR (300
MHz, CD3OD) δ 1.64 (m, 4H), 1.91 (m, 2H), 2.11 (m, 2H), 2.64
(m, 1H), 2.89 (m, 1H), 3.30 (m, 2H), 3.67 (t, J ) 6.6 Hz, 2H),
3.89 (m, 1H), 4.16 (s, 3H), 5.10 (br s, 2H), 5.80 (d, J ) 2.6 Hz,
1H), 7.58 (m, 2H), 7.89 (d, J ) 4.8 Hz, 1H), 8.11 (d, J ) 10.3
Hz, 1H), 8.87 (d, J ) 4.8 Hz, 1H). 13C NMR (75 MHz, CD3OD)
δ 21.5, 27.3, 28.7, 33.1, 38.6, 44.1, 56.4, 59.3, 60.9, 61.0, 72.3,
102.5, 120.0, 123.3, 128.1, 131.4, 144.7, 148.1, 150.6, 159.7.
IR (KBr) 3450, 1600, 1580, 1520, 1445, 1355, 1245, 1190, 1105,
1050 cm-1. Anal. Calcd for C20H26O3N2 (342.43): C, 70.15; H,
7.65; N, 8.18. Found: C, 69.08; H, 7.99; N, 7.66. HRMS (CI,
CH4) calcd for C20H27O3N2 [MH+] 343.2022, found 343.2024.
Rea ction s w ith TEMP O. Meth od E: Catecholborane
(0.64 mL, 6.0 mmol) was added dropwise at 0 °C under N2 to
a solution of the olefin (3.0 mmol) and N,N-dimethylacetamide
(28.0 µL, 0.3 mmol) in CH2Cl2 (2 mL), and the reaction mixture
was heated under reflux for 3 h. EtOH (0.21 mL, 3.6 mmol)
was added at 0-5 °C and the solution was stirred for 15 min
at room temperature. To this solution were successively added
TEMPO (1.03 g, 6.6 mmol) in CH2Cl2 (4 mL) and DMPU (0.36
mL, 3.0 mmol). The reaction was stirred overnight at room
temperature. The resulting mixture was treated with satu-
rated aqueous NaHCO3 solution and extracted with Et2O. The
organic layer was dried (MgSO4), filtered, and concentrated.
The crude product was purified by flash chromatography
(hexane, hexane/diethyl ether).
4-(Ben zyloxy)b u t a n ol (12a )50 a n d 3-(Ben zyloxy)b u -
ta n ol (12b).51 Prepared according to method B from 8 (486
(48) Alexakis, A.; J achiet, D.; Normant, J . F. Tetrahedron 1986, 42,
5607-5620.
(49) Ley, S. V.; Parra, M.; Redgrave, A. J .; Sternfeld, F. Tetrahedron
1990, 46, 4994-5026.
(50) Garcia, C.; Martin, T.; Martin, V. J . Org. Chem. 2001, 66, 1420-
1428.
(51) Castra, P.; Danzin, C.; Metclaf, B.; J ung, M. J . Chem. Soc.,
Perkin Trans. 1 1985, 2201-2208.
7200 J . Org. Chem., Vol. 67, No. 21, 2002