The Journal of Organic Chemistry
Article
2-(2-(4-Chlorophenyl)-2-hydroxyethyl)bicyclo[2.1.1]hexan-1-ol
(5f). White solid (179 mg, 71% yield), mp 98−100 °C; 1H NMR (600
MHz, CDCl3) δ 7.32−7.28 (m, 4H), 4.72−4.70 (m, 1H), 2.10−2.03
(m, 3H), 1.91−1.85 (m, 1H), 1.75−1.72 (m, 1H), 1.61−1.59 (m, 1H),
1.58−1.49 (m, 2H), 1.43−1.42 (m, 1H), 1.14−1.13 (m, 1H); 13C
NMR (100 MHz, CDCl3) δ 143.6, 133.0, 128.5, 127.0, 80.3, 74.6, 46.5,
43.7, 41.0, 39.9, 38.2, 27.9. HRMS (ESI) m/z: calcd for
C14H17ClO2Na [M + Na]+: 275.0809; found: 275.0814.
2-(2-(3-Chlorophenyl)-2-hydroxyethyl)bicyclo[2.1.1]hexan-1-ol
(5g). White solid (152 mg, 60% yield), mp 91−93 °C; 1H NMR (600
MHz, CDCl3) δ 7.39−7.34 (m, 3H), 7.30−7.26 (m, 1H), 5.76 (b, s,
1H), 4.76 (dd, J = 10.5, 1.8 Hz, 1H), 4.18 (b, s, 1H), 2.14−2.11 (m,
1H), 2.09−2.04 (m, 2H), 1.97−1.91 (m, 1H), 1.79−1.76 (m, 1H),
1.63−1.61 (m, 1H), 1.58−1.55 (m, 1H), 1.51−1.49 (m, 1H), 1.44−
1.43 (m, 1H), 1.15−1.13 (m, 1H); 13C NMR (150 MHz, CDCl3) δ
145.1, 128.5, 127.5, 125.7, 80.4, 75.5, 46.4, 43.6, 41.0, 40.1, 38.3, 27.9.
HRMS (ESI) m/z: calcd for C14H17ClO2Na [M + Na]+: 275.0809;
found: 275.0816.
1.61 (m, 1H), 1.56−1.52 (m, 1H), 1.46−1.42 (m, 2H), 1.15−1.12 (m,
1H), 0.96−0.90 (m, 1H), 0.52−0.49 (m, 2H), 0.33−0.28 (m, 1H),
0.21−0.19 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 80.3, 78.0, 46.4,
40.8, 40.4, 39.7, 38.2, 27.9, 18.5, 3.3, 2.7. HRMS (ESI) m/z: calcd for
C11H18O2Na [M + Na]+: 205.1199; found: 205.1199.
2-(2-Hydroxypentyl)bicyclo[2.1.1]hexan-1-ol (5n). White solid
1
(140 mg, 76% yield), mp 76−78 °C; H NMR (600 MHz, CDCl3)
δ 3.70−3.66 (m, 1H), 2.08−2.07 (m, 1H), 2.03−1.99 (m, 1H), 1.97−
1.94 (m, 1H), 1.64−1.62 (m, 1H), 1.60−1.59 (m, 1H), 1.57−1.53 (m,
2H), 1.51−1.46 (m, 2H), 1.45−1.41 (m, 3H), 1.39−1.34 (m, 1H),
1.14−1.12 (m, 1H), 0.95−0.93 (m, 3H); 13C NMR (150 MHz,
CDCl3) δ 80.3, 72.5, 46.5, 40.8, 40.7, 40.5, 39.7, 38.1, 27.9, 18.9, 14.1.
HRMS (ESI) m/z: calcd for C11H20O2Na [M + Na]+: 207.1356;
found: 207.1351.
2-(2-Hydroxy-3-methylbutyl)bicyclo[2.1.1]hexan-1-ol (5o). White
solid (153 mg, 83% yield), mp 77−79 °C; 1H NMR (400 MHz,
CDCl3) δ 5.86 (s, 1H), 3.64 (b, s, 1H), 3.49−3.44 (m, 1H), 2.07−1.98
(m, 2H), 1.96−1.90 (m, 1H), 1.70−1.66 (m, 1H), 1.63−1.60 (m, 1H),
1.56−1.51 (m, 3H), 1.48−1.44 (m, 1H), 1.42−1.41 (m, 1H), 1.14−
1.12 (m, 1H), 0.93−0.91 (m, 6H); 13C NMR (100 MHz, CDCl3) δ
80.4, 77.7, 46.4, 40.9, 39.8, 38.2, 36.9, 34.4, 27.9, 18.5, 17.6. HRMS
(ESI) m/z: calcd for C11H20O2Na [M + Na]+: 207.1355; found:
207.1358.
2-(2-(2-Chlorophenyl)-2-hydroxyethyl)bicyclo[2.1.1]hexan-1-ol
1
(5h). White solid (167 mg, 66% yield), mp 120−121 °C; H NMR
(600 MHz, CDCl3) δ 7.59−7.57(m, 1H), 7.28−7.23 (m, 2H), 7.17−
7.14 (m, 1H), 5.95 (b, s, 1H), 5.09 (d, J = 10.0 Hz, 1H), 4.98 (b, s,
1H), 2.14−2.11 (m, 1H), 2.05−2.02 (m, 2H), 1.85−1.82 (m, 1H),
1.71−1.65 (m, 1H), 1.53−1.49 (m, 2H), 1.46−1.44 (m, 1H), 1.36−
1.35 (m, 1H), 1.13−1.12 (m, 1H); 13C NMR (150 MHz, CDCl3) δ
142.5, 131.4, 129.2, 128.2, 127.1, 126.8, 80.2, 71.4, 46.3, 41.7, 40.9,
39.9, 37.9, 27.9. HRMS (ESI) m/z: calcd for C14H17ClO2Na [M +
Na]+: 275.0809; found: 275.0810.
2-(2-Cyclohexyl-2-hydroxyethyl)bicyclo[2.1.1]hexan-1-ol (5p).
White solid (153 mg, 68% yield), mp 87−90 °C; 1H NMR (400
MHz, CDCl3) δ 5.72 (b, s, 1H), 3.50−3.46 (m, 1H), 3.21 (b, s, 1H),
2.08−2.01 (m, 2H), 1.96−1.90 (m, 1H), 1.80−1.67 (m, 5H), 1.66−
1.58 (m, 3H), 1.57−1.52 (m, 1H), 1.50−1.46 (m, 1H), 1.44−1.43 (m,
1H), 1.38−1.32 (m, 1H), 1.27−1.19 (m, 2H), 1.16−1.13 (m, 2H),
1.11−0.99 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 80.4, 46.4, 44.6,
41.0, 39.9, 38.3, 37.3, 29.1, 28.0, 27.8, 26.5, 26.3, 26.2. HRMS (ESI)
2-(2-(4-Fluorophenyl)-2-hydroxyethyl)bicyclo[2.1.1]hexan-1-ol
1
(5i). White solid (180 mg, 76% yield), mp 94−96 °C; H NMR (400
MHz, CDCl3) δ 7.32−7.28 (m, 2H), 7.02−6.98 (m, 2H), 5.65 (b, s,
1H), 4.71−4.68 (m, 1H), 4.60 (b, s, 1H), 2.10−2.00 (m, 3H), 1.91−
1.83 (m, 1H), 1.73−1.69 (m, 1H), 1.57−1.52 (m, 2H), 1.48−1.44 (m,
1H), 1.40 (s, 1H), 1.12−1.10 (m, 1H); 13C NMR (100 MHz, CDCl3)
δ 162.1 (d, JC−F = 243.4 Hz, 1C), 141.0 (d, JC−F = 3.1 Hz, 1C), 127.2
(d, JC−F = 8.0 Hz, 1C), 115.1 (d, JC−F = 21.2 Hz, 1C), 80.3, 74.6, 46.5,
43.7, 41.0, 39.9, 38.1, 27.9. HRMS (ESI) m/z: calcd for C14H17FO2Na
[M + Na]+: 259.1105; found: 259.1108.
+
m/z: calcd for C14H24O2 Na [M + Na]+: 247.1669; found: 247.1662.
2-(2-Hydroxy-3-phenylpropyl)bicyclo[2.1.1]hexan-1-ol (5q).
1
White solid (174 mg, 75% yield), mp 98−101 °C; H NMR (600
MHz, CDCl3) δ 7.36−7.33 (m, 2H), 7.29−7.23 (m, 3H), 5.50 (s, 1H),
3.94−3.91 (m, 1H), 3.19 (s, 1H), 2.86−2.83 (m, 1H), 2.77−2.73 (m,
1H), 2.09 (s, 1H), 2.05−1.96 (m, 2H), 1.75−1.67 (m, 2H), 1.65−1.63
(m, 1H), 1.58−1.55 (m, 1H), 1.49−1.47 (m, 1H), 1.44 (s, 1H), 1.16−
1.14 (m, 1H). 13C NMR (150 MHz, CDCl3) δ 138.2, 129.4, 128.7,
126.7, 80.4, 73.8, 46.4, 44.8, 40.9, 40.2, 39.6, 38.3, 27.9. HRMS (ESI)
2-(2-([1,1′-Biphenyl]-3-yl)-2-hydroxyethyl)bicyclo[2.1.1]hexan-1-
1
ol (5j). White solid (200 mg, 68% yield), mp 99−102 °C; H NMR
+
m/z: calcd for C15H20O2 Na [M + Na]+: 255.1356; found: 255.1362.
(600 MHz, CDCl3) δ 7.61−7.58 (m, 4H), 7.47−7.45 (m, 4H), 7.39−
7.36 (m, 1H), 5.49 (b, s, 1H), 4.83 (dd, J = 10.4, 1.6 Hz, 1H), 4.02 (b,
s, 1H), 2.19−2.16 (m, 1H), 2.11−2.07 (m, 2H), 2.03−1.97 (m, 1H),
1.85−1.82 (m, 1H), 1.68−1.66 (m, 1H), 1.62−1.59 (m, 1H), 1.56−
1.53 (m, 1H), 1.49−1.48 (m, 1H), 1.19−1.17 (m, 1H). 13C NMR
(150 MHz, CDCl3) δ 144.1, 140.8, 140.5, 128.8, 127.3, 127.2, 127.1,
126.1, 80.5, 75.3, 46.5, 43.6, 41.1, 40.1, 38.3, 27.9. HRMS (ESI) m/z:
calcd for C20H22O2Na [M + Na]+: 317.1512; found: 317.1515.
2-(2-(Furan-2-yl)-2-hydroxyethyl)bicyclo[2.1.1]hexan-1-ol (5k).
White solid (52 mg, 25% yield), mp 75−78 °C; 1H NMR (600
MHz, CDCl3) δ 7.37−7.36 (m, 1H), 6.34−6.33 (m, 1H), 6.25−6.24
(m, 1H), 4.79−4.77 (m, 1H), 2.12−2.10 (m, 1H), 2.08−2.02 (m, 3H),
1.97−1.93 (m, 1H), 1.64−1.58 (m, 2H), 1.52−1.49 (m, 1H), 1.46−
1.45 (m, 1H), 1.20−1.18 (m, 1H); 13C NMR (150 MHz, CDCl3) δ
156.9, 141.7, 110.2, 105.3, 80.3, 68.4, 46.4, 40.9, 39.4, 39.2, 37.8, 28.0.
HRMS (ESI) m/z: calcd for C12H16O3Na [M + Na]+: 231.0992;
found: 231.0998.
(E)-2-(2-Hydroxypent-3-en-1-yl)bicyclo[2.1.1]hexan-1-ol (5r).
White solid (109 mg, 60% yield), mp 80−82 °C; 1H NMR (400
MHz, CDCl3) δ 5.71−5.62 (m, 1H), 5.56−5.50 (m, 1H), 4.15−4.11
(m, 1H), 2.07−1.98 (m, 3H), 1.69−1.66 (m, 4H), 1.63−1.58 (m, 2H),
1.54−1.51 (m, 1H), 1.48−1.44 (m, 1H), 1.43−1.41 (m, 1H), 1.14−
1.12 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 134.4, 126.1, 80.3,
73.7, 46.4, 41.1, 40.9, 39.6, 38.2, 27.9, 17.6. HRMS (ESI) m/z: calcd
for C11H18O2Na [M + Na]+: 205.1199; found: 205.1198.
2-(2-Hydroxy-2-phenylpropyl)bicyclo[2.1.1]hexan-1-ol (5s).
1
White solid (121 mg, 52% yield), mp 111−113 °C; H NMR (600
MHz, CDCl3) δ 7.52−7.51 (m, 2H), 7.39−7.36 (m, 2H), 7.29−7.27
(m, 1H), 4.97 (b, s, 1H), 3.18 (b, s, 1H), 2.29−2.26 (m, 1H), 2.11−
2.10 (m, 1H), 2.09−2.01(m, 2H), 1.84−1.81 (m, 1H), 1.70 (s, 3H),
1.68 (s, 1H), 1.59−1.53 (m, 2H), 1.44−1.43 (m, 1H), 1.18−1.16 (m,
1H); 13C NMR (150 MHz, CDCl3) δ 149. 7, 128.3, 126.8, 124.5, 80.5,
75.0, 47.8, 46.5, 40.9, 38.6, 35.9, 28.0, 27.7. HRMS (ESI) m/z: calcd
for C15H20O2Na [M + Na]+: 255.1356; found: 255.1359.
2-(1-Hydroxy-2-methyl-1-phenylpropan-2-yl)bicyclo[2.1.1]-
hexan-1-ol (5l). White solid (111 mg, 45% yield), mp 115−117 °C;
1H NMR (600 MHz, CDCl3) δ 7.29−7.28 (m, 4H), 7.26−7.24 (m,
1H), 4.49 (s, 1H), 2.01 (s, 1H), 1.96−1.94 (m, 1H), 1.84−1.80 (m,
1H), 1.74−1.72 (m, 1H), 1.53−1.50 (m, 1H), 1.46−1.44 (m, 2H),
1.27 (s, 1H), 0.92 (s, 3H), 0.54 (s, 3H); 13C NMR (150 MHz, CDCl3)
δ 142.2, 128.3, 127.6, 127.4, 83.9, 80.4, 51.3, 48.7, 41.6, 41.1, 33.7,
26.5, 25.9, 14.6. HRMS (ESI) m/z: calcd for C16H22O2Na [M + Na]+:
269.1512; found: 269.1516.
2-((1-Hydroxycyclohexyl)methyl)bicyclo[2.1.1]hexan-1-ol (5t).
1
White solid (38 mg, 18% yield), mp 113−115 °C; H NMR (600
MHz, CDCl3) δ 5.42 (s, 1H), 2.62 (s, 1H), 2.17−2.16 (m, 1H), 2.10−
2.09 (m, 1H), 2.05−2.02 (m, 1H), 1.77−1.72 (m, 2H), 1.69−1.68 (m,
2H), 1.67−1.65 (m, 1H), 1.60−1.57 (m, 2H), 1.56−1.54 (m, 4H),
1.52−1.49 (m, 3H), 1.42−1.41 (m, 1H), 1.34−1.28 (s, 1H), 1.15−
1.14 (m, 1H); 13C NMR (150 MHz, CDCl3) δ 80.5, 72.2, 46.4, 40.7,
40.3, 38.6, 35.4, 34. 6, 28.0, 25.7, 22.6, 22.2. HRMS (ESI) m/z: calcd
for C13H22O2 Na [M + Na]+: 233.1512; found: 233.1518.
2-(2-Cyclopropyl-2-hydroxyethyl)bicyclo[2.1.1]hexan-1-ol (5m).
1
White solid (129 mg, 71% yield), mp 97−100 °C; H NMR (400
Preparation of the CuCl2·2H2O/allylSmBr/HMPA/THF Sys-
tem. To a two-necked flask containing samarium powder (0.7 g, 4.67
mmol) were added THF (30 mL) and allyl bromide (0.4 g, 3.3 mmol)
MHz, CDCl3) δ 5.86 (b, s, 1H), 3.66 (b, s, 1H), 2.94−2.90 (m, 1H),
2.06−1.98 (m, 2H), 1.92−1.88 (m, 1H), 1.77−1.69 (m, 2H), 1.63−
H
dx.doi.org/10.1021/jo501797w | J. Org. Chem. XXXX, XXX, XXX−XXX