Notes
J . Org. Chem., Vol. 65, No. 23, 2000 8125
[
2(1′R),4R,5R]-4,5-Dicycloh exyl-2-[1-(p en ta flu or op h en yl-
(R)-1-[(4-Tr iflu or om eth yl)p h en yl]-2-p h en yleth a n ol (4e):
yield 80%; mp 57-58 °C; [R]5 22 ) +18.5 (c ) 1.200, CHCl
46
); ee
)
[
1
0
2
eth yl]-1,3,2-d ioxa bor ola n e (3g): Yield, 89%; viscous liquid;
3
5
46
R] 22 ) -15.5 (c ) 1.152, CHCl
3
); IR (KBr) 2927, 1653, 1498,
> 99%; IR (KBr) 3396, 2926, 1618, 1494, 1448, 1417, 1326, 1165,
1
451, 1355, 1394, 1234, 1195, 967 cm-1
.80-1.75 (multiplet with a doublet at 1.30, 25H, J ) 7.5 Hz),
.76 (q, 1H, J ) 7.6 Hz), 3.85 (m, 2H); 19F NMR (CDCl
) δ
;
1
H NMR (CDCl
) δ
-1
3
3
1124, 1067 cm ; H NMR (CDCl ) δ 2.13 (s, 1H), 2.90 (dd, 2H,
J ) 5 Hz), 3.02 (dd, 1H, J ) 5.0 Hz), 4.91 (dd, 1H, J ) 5 Hz),
3
7.0-7.4 (m, 5H), 7.42, (d, 2H, J ) 8 Hz), 7.57 (d, 2H, J ) 8 Hz);
19
13
-
163.76 (m, 2F), 158.51 (t, 1F, J ) 20 Hz), -143.42 (m, 2F); 13
C
F NMR (CDCl
3
3
) δ -62.57 (s, 3F); C NMR (CDCl ) δ 46.05,
NMR (CDCl
3
) δ 17.0, 25.80, 25.94, 26.44, 27.52, 28.42, 33.51,
74.61, 124.30 (q, J C-F ) 282 Hz), 125.24, 125.31, 126.15, 126.86,
128.62, 129.48, 137.28, 147.6; MS (EI) m/z (species, rel int)
O, 2), 175 (M - PhCH
+ H, 100), 91 (PhCH
(Ph , 4).
(R)-1-[3,5-Bis(t r iflu or om e t h yl)p h e n yl]-2-p h e n yle t h a -
n ol (4f): yield 84%; viscous liquid; [R] 22 ) +17.4 (c ) 1.113,
CHCl ); ee > 99%; IR (KBr) 3408, 2931, 1707, 1614, 1462, 1384,
1278, 1173, 1134, 1076, 943 cm ; H NMR (CDCl
4
2.96, 84.27, 118.70, 134.96, 139.95, 147.39; MS (EI) m/z (species,
rel int) 430 (M , 41), 347 (M - C
+
+
+
+
+
+
6
H
11, 100), 191 [(C
6
H
11
)
2
CHC ,
267 (M + H, 1), 248 (M -H
2
2
, 19),
, 50), 77
+
+
+
+
1
5)], 83 (C
found 430.2117.
2(1′R),4R,5R]-4,5-Dicycloh exyl-2-[1-(4-flu or op h en yl)-
eth yl]-1,3,2-d ioxa bor ola n e (3h ): yield 92%; viscous liquid;
6
H
11 , 92); HRMS calcd for C22
H
28
F
5
O
2
B (M ) 430.2102,
145 (CF
3
C
6
H
4
, 5), 92 (PhCH
2
2
+
[
5
46
5
46 2
[
R]
2
) -16.4 (c ) 1220, CHCl
3
); IR (KBr) 2926, 1601, 1506,
3
1
-1
1
1
0
2
-
2
1
450, 1353, 1223, 1157, 1094, 985 cm-1
:
H NMR (CDCl
3
) δ
3
) δ 2.36 (s,
.80-1.74 (multiplet with a doublet at 1.31, 25H, J ) 7.5 Hz),
1H), 2.92 (dd, 2H, J ) 5 Hz), 3.02 (dd, 1H, J ) 5.0 Hz), 4.99 (t,
1
9
19
.45 (q, 1H, J ) 7.5 Hz), 3.84 (m, 2H); F NMR (CDCl
3
) δ
1H, J ) 5 Hz), 7.1 (m, 1H), 7.26, (m, 2H,), 7.77 (s, 1H); F NMR
1
3
13
119.21 (t, 1F, J ) 12.5 Hz), C NMR (CDCl
3
) δ 17.19, 24.00,
(CDCl
3
3
) δ -63.08 (s, 6F); C NMR (CDCl ) δ 46.10, 74.13,
5.87, 25.97, 26.45, 27.25, 28.20, 83.44, 114.75, 128.87, 140.61,
115.83, 120.62, 124.0 (q, J C-F ) 283.5), 121.44, 126.07, 127.22,
+
58.45, 163.27; MS (EI) m/z (species, rel int) 458 (M , 46), 375
128.83, 129.28, 129.47, 130.62, 131.29, 131.94, 132.61, 133.22;
+
+
+
+
(
4
M
- CH
3
, 18), 123 [CH
3
CH(C
6
H
4
F), 18], 107 (M - C
6
H
4
FC,
MS (EI) m/z (species, rel int) 334 (M , 1), 316 (M - H
2
O, 1),
+
+
+
+
+
1) 83 (C
6
H
11 , 51); HRMS calcd for C22
H
32FO
2
B (M ) 358.2479,
315 (M - F, 1), 243 (M -C
6
H
5
CH
2
, 10), 195 [M - (CF
3
+ CF
3
3
+
+
found 358.2479.
2(1′R),4R,5R]-4,5-Dicycloh exyl-2-[1-[4-(tr iflu or om eth yl)-
p h en yl]eth yl]-1,3,2-d ioxa bor ola n e (3i): yield 91%; viscous
+ H), 13], 92 (PhCH
2
+ H, 100), 91 (PhCH
2
, 67), 69 (CF
, 2).
[
Anal. Calcd for C16
H, 3.98.
H
12
F
6
O: C, 57.47; H, 3.62. Found: C, 57.57;
5
46
16
liquid; [R] 22 ) -13 (c ) 1.415, CHCl
3
); IR (KBr) 2926, 1695,
(R)-1-(P en ta flu or op h en yl)eth a n ol (4g): yield 86%; mp
41 °C; [R] 22 ) +13 (c ) 1.130, CHCl
3365, 1653, 1505,1304, 1134, 1084, 1043, 973, 936, 865 cm
546
1
618, 1452, 1408, 1323, 1236, 1166, 891 cm-1; 1H NMR (CDCl
3
)
3
); ee > 99%; IR (KBr)
-
1
δ 0.80-1.74 (multiplet with a doublet at 1.29, 25H, J ) 7.5 Hz),
;
1
2
7
(
.74 (q, 1H, J ) 7.5 Hz), 3.82 (m, 2H), 7.44 (d, 2H, J ) 8 Hz),
H NMR (CDCl
5.22 (q, 1H, J ) 6.7 Hz); F NMR (CDCl
155.76 (t, 1F, J ) 20.5 Hz), - 144.80 (m, 2); C NMR (CDCl
δ 23.16, 62.28, 118.10, 136.12, 139.35, 143.25, 146.50; MS (EI)
3
) δ 1.62 (d, 3H, J ) 6.7 Hz), 2.18 (broad, s, 1H),
.55 (d, 2H, J ) 8 Hz); 19F NMR (CDCl
) δ -62.10 (s, 3F); MS
19
) δ -162.15 (m, 2F),
13
3
3
+
+
EI) m/z (species, rel int) 408 (M , 41), 325 (M - C
6
H
11, 100),
3
)
+
+
1
91 [(C
2(1′R),4R,5R]-4,5-Dicycloh exyl-2-[1-[3,5-b is(t r iflu or o-
m eth yl)p h en yl]eth yl]-1,3,2-d ioxa bor ola n e (3j): yield 89%;
6 11 2 6
H ) CHC , 12)], 83 (C H11 , 78).
+
+
[
m/z (species, rel int) 212 (M , 10), 197 (M - CH
3
, 100), 195
CHOH , 10). Anal. Calcd
8 5 5
H F O: C, 45.28; H, 2.38. Found: C, 45.28; H, 2.38.
+
+
6 5 3
F , 4), 45 (CH
+
(M - OH, 8), 167 (C
for C
(R)-1-(4-F lu or op h en yl)eth a n ol (4h ): yield 85%; viscous
5
46
viscous liquid; [R] 22 ) -12 (c ) 1.140, CHCl
652, 1600, 1490, 1450, 1358, 1110, 889 cm ; H NMR (CDCl )
3
3
); IR (KBr) 2922,
1
-
1
17
1
liquid; [R]5 22 ) +27 (c ) 1.270, CHCl
46
); ee > 99%; IR (film)
δ 0.80-1.76 (multiplet with a doublet at 1.28, 25H, J ) 7.5 Hz),
3
-
1
2
1
.72 (q, 1H, J ) 7.5 Hz), 3.84 (m, 2H), 7.50 (m, 2H), 7.75 (m,
3367, 2962, 1657, 1500,1306, 1138, 1081, 1040, 978, 934 cm
;
1
9
1
H); F NMR (CDCl
3
) δ -63.04 (s, 3F), -63.07 (s, 3F); MS (EI)
H NMR (CDCl
3
) δ 1.50 (d, 3H, J ) 6.5 Hz), 2.0 (broad, s, 1H),
+
+
m/z (species, rel int) 476 (M , 22), 393 (M - C
6
H
11, 100), 191
4.95 (q, 1H, J ) 6.5 Hz), 6.6 (d, 2H, J ) 6 Hz), 7.50 (d, 2H, J )
+
+
+
19
[
(C
6
H
11
)
H
2
CHC , 17)], 83 (C
6
H
11 , 12), 69 (CF
3
, 5); HRMS calcd
3
6 Hz); F NMR (CDCl ) δ -118.20 (m, 1F); MS (El) m/z (species,
+
+
+
+
for C24
31
F
6
O
2
B (M ) 476.2321, found 476.2318.
rel int) 140 (M , 8), 125 (M - CH
3
, 100), 123 (M - OH, 7).
17
Gen er a l P r oced u r e for th e Syn th esis of r-F lu or in a ted
Ar yl Alcoh ols. Aqueous 3 M sodium hydroxide (25 mL) and a
solution of boronic esters (3c-j, 8 mmol) in diethyl ether (150
mL) were stirred and cooled with an ice bath during the
portionwise addition of 30% hydrogen peroxide (25 mL) over a
period of 1 h. The reaction mixture was stirred for 15 h. More
ether (100 mL) was added. The ether phase was washed with
water, dried over magnesium sulfate and filtered. Removal of
ether at low pressure yielded a mixture of alcohols (4c-j) and
(R)-1-[4-(Tr iflu or om et h yl)p h en yl]et h a n ol
(4i): yield
); ee > 99%;
80%; viscous liquid; [R]5 22 ) +28 (c ) 1.115, CHCl
46
3
-
1
IR (KBr) 3360, 1650, 1496,1300, 1130, 1088, 1045, 970 cm
;
1
H NMR (CDCl ) δ 1.50 (d, 3H, J ) 6.6 Hz), 2.20 (broad, s, 1H),
3
5.0 (q, 1H, J ) 6.6 Hz), 7.50 (d, 2H, J ) 8.8 Hz), 7.65 (d, 2H, J
) 8.8 Hz); 19F NMR (CDCl
) δ -63.0 (s, 3F); MS (EI) m/z (species,
3
+
+
+
rel int) 190 (M , 8), 175 (M - CH
3
, 100), 173 (M - OH, 7), 69
+
3
, 8).
(CF
(R)-1-[3,5-Bis(tr iflu or om eth yl)p h en yl]eth a n ol (4j): yield
82%; viscous liquid; [R]5 22 ) +16 (c ) 1.204, CHCl
46
); ee > 99%;
[
(R)-(R*,R*)]-1,2-dicyclohexyl-1,2-ethanediol. The latter was re-
3
-
1 1
covered in ∼90% yield by addition of pentane (15 mL) and
crystallization at 0 °C. Fluorinated aryl alcohols were isolated
in >79% yield by using column chromatography eluting with
ether/pentane (1:3) mixture.
IR (film) 3368, 1658, 1500, 1298, 1138, 1080, 968, cm ; H NMR
(CDCl ) δ 1.50 (d, 3H, J ) 6.6 Hz), 2.40 (broad, s, 1H), 4.90 (q,
1H, J ) 6.6 Hz) 7.20, (m, 2H,), 7.75 (s, 1H); F NMR (CDCl
-63.01 (s, 3F), - 63.05 (s, 3F); MS (EI) m/z (species, rel int) 258
3
1
9
3
) δ
+
+
+
+
3
(
R)-1-(P en ta flu or op h en yl)-2-p h en yleth a n ol (4c): yield
(M , 10), 243 (M - CH
3
, 100), 226 (M - OH, 8), 69(CF
, 14).
5
46
8
(
9%; mp 58-59 °C; [R] 22 ) +20 (c ) 2.3, CHCl
3
); ee > 99%;
Ack n ow led gm en t. This work was supported by the
National Science Foundation (Grant No. CHE-9720365).
We are thankful to Dr. G. Knerr for obtaining high-
resolution mass spectra.
KBr) 3169, 2920, 1651, 1499, 1451, 1357, 1123, 1064, 999, 954
-
1 1
cm ; H NMR (CDCl
3
) δ 2.18 (s, 1H), 3.07 (dd, 1H, J ) 6.5 Hz),
3
5
2
1
.29 (dd, 1H, J ) 8 Hz), 5.25 (t, 1H, J ) 6.5 Hz), 7.0-7.35 (m,
1
9
3
H); F NMR (CDCl ) δ -162.01 (m, 2F), -154.97 (t, 1F, J )
1
3
0 Hz), -143.59 (m, 2); C NMR (CDCl
3
) δ 43.14, 67.37, 116.24,
Su p p or t in g In for m a t ion Ava ila b le: Crystal data and
structure refinement, atomic coordinates, bond lengths and
bond angles, anisotropic displacement parameters, hydrogen
coordinates, and crystal packing diagram for 3c. This material
is available free of charge via the Internet at http://pubs.org.
27.18, 128.75, 129.11, 134.92, 141.00, 142.50, 147.32; MS (EI)
+
+
m/z (species, rel int) 288 (M , 1), 197 (M - PhCH
2
, 40), 92
, 88). Anal. Calcd for C14
C, 58.34; H, 3.15. Found: C, 58.42; H, 3.02.
R)-1-(4-F lu or op h en yl)-2-p h en yleth a n ol (4d ): yield 82%;
+
(
PhCH
2
+ H, 100), 91 (PhCH
2
9 50
H F :
(
5
46
mp 67 °C; [R] 22 ) +22 (c ) 1.140, CHCl
3
); ee > 99%; IR (KBr)
J O005622H
1
3
400, 2926, 1495, 1445, 1406, 1370, 1240, 1030, 985 cm-1; H
(16) Vorozhtsov, N. N., J r.; Barkhash, V. A.; Ivanova, N. G.;
NMR (CDCl ) 1.70 (s, 1H), 2.94 (dd, 1H, J ) 7 Hz), 3.0 (dd, 1H,
3
Anichkina, S. A.; Andreev-Skaya, O. I. Dokl. Akad. Nauk SSSR 1964,
J ) 7 Hz), 4.95 (t, 1H, J ) 8.6 Hz), 4.86 (t, 1H, J ) 6.0 Hz),
1
59, 125-128.
17) (A) Nieduzak, T. R.; Margolin, A. L. Tetrhedron: Asymmetry
6
(
-
.80-7.34 (m, 9H); 19F NMR (CDCl
3
) δ -115.20 (m, 1F,); MS
(
+
+
+
EI) m/z (species, rel int) 216 (M , 2), 199 (M -OH, 2), 125 (M
1
991, 2, 113-122. (b) Mathre, D. J .; Thompson, A. W.; Douglas, A.
W.; Hoogsteen, K.; Carroll, J . D.; Corley, E. G.; Grabowski, E. J . J . J .
Org. Chem. 1993, 58, 2880-2888.
+
+
PhCH
for C14
2
, 99), 92 (PhCH
2
+ H, 100), 77 (Ph , 17). Anal. Calcd
H13FO: C, 77.74; H, 6.06. Found: C, 77.53; H, 6.18.