4422
M. Hatano et al. / Tetrahedron 67 (2011) 4417e4424
(EIþ) calcd for C9H14O2 [M]þ 154.0994, found 154.0995. Chiral GC CP-
hexane, toluene, EtOAc, etc.) (10 mL) and satd NH4Cl aqueous so-
lution (10 mL) were poured into the mixture at 0 ꢀC. The product
was extracted with ether or EtOAc (10 mLꢁ3) and washed by brine
(10 mL). The combined extracts were dried over MgSO4. The or-
ganic phase was concentrated under reduced pressure and the
crude product was purified by neutral silica gel column chroma-
tography (eluent: hexane/EtOAc¼20/1 to 1/2), to give the desired
products (6). The enantiomeric purity was determined by GC or
HPLC on chiral column.
Cyclodextrin-
b
-2,3,6-M-19, 95 ꢀC, tR¼11.6 min (major, S), 12.1 min
(minor, R).
4.3.8. (S)-2-(Thiophen-2-yl)butan-2-ol (3h)10a
.
1H NMR (400 MHz,
CDCl3)
d
0.87 (t, J¼7.5 Hz, 3H),1.60 (s, 3H),1.88 (q, J¼7.5 Hz, 2H), 2.18
(br, 1H), 6.89 (dd, J¼3.6, 1.5 Hz, 1H), 6.93 (dd, J¼4.8, 3.6 Hz, 1H), 7.17
(dd, J¼4.8, 1.2 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d 8.5, 29.6, 37.4,
74.0,122.3,123.6,126.5,153.2. IR (neat) 3408, 2971, 2932,1457,1375,
1235,1125 cmꢂ1. HRMS (FABþ) calcd for C8H11S [MꢂOH]þ 139.0581,
found 139.0580. Chiral HPLC OD-H, n-hexane/i-PrOH¼98/2, 0.4 mL/
min, tR¼26.6 min (minor, R), 29.4 min (major, S).
4.5. Analytical data for the Ph-adducts
4.5.1. (S)-1-(4-Chlorophenyl)-1-phenylethanol (6a)10a
MHz, CDCl3)
1.87 (s, 3H), 2.38 (br, 1H), 7.18e7.40 (m, 9H). 13C NMR
(100 MHz, CDCl3) d 30.7, 75.8, 125.8, 127.2, 127.3, 128.2, 128.3, 132.7,
.
1H NMR (400
4.3.9. (S)-3-Methyl-1-phenylpentan-3-ol (3i)17
.
1H NMR (400 MHz,
d
CDCl3)
d
0.92 (t, J¼7.5 Hz, 3H), 1.21 (s, 3H), 1.39 (br, 1H), 1.55 (q,
J¼7.5 Hz, 2H),1.75 (m, 2H), 2.67 (m, 2H), 7.12e7.32 (m, 5H). 13C NMR
146.6, 147.5. IR (neat) 3419, 2979, 1489, 1446, 1093, 1013 cmꢂ1. HRMS
(FABþ) calcd for C14H12Cl [MꢂOH]þ 215.0628, found 215.0626. Chiral
GC CHIRALDEX B-DM, 150 ꢀC, tR¼30.6 min (major, S), 31.9 min (mi-
nor, R).
(100 MHz, CDCl3)
d 8.3, 26.3, 30.3, 34.4, 43.2, 72.8, 125.7, 128.3,
128.4, 142.6. IR (neat) 3389, 2966, 2936, 1455, 1375, 1147 cmꢂ1
.
HRMS (FABþ) calcd for C12H17 [MꢂOH]þ 161.1330, found 161.1334.
Chiral GC CHIRALDEX B-DM, 100 ꢀC, tR¼36.1 min (major, S),
38.2 min (minor, R).
4.5.2. (S)-1-(4-Methoxyphenyl)-1-phenylethanol (6b)10a
(400 MHz, CDCl3) 1.91 (s, 3H), 2.21 (br, 1H), 3.77 (s, 3H), 6.78e6.87
(m, 2H), 7.18e7.44 (m, 7H). 13C NMR (100 MHz, CDCl3)
31.0, 55.2,
.
1H NMR
d
4.3.10. (S)-3,7-Dimethyloctan-3-ol (3j)18
.
1H NMR (400 MHz,
d
CDCl3)
d
0.88 (d, J¼6.9 Hz, 6H), 0.89 (t, J¼7.2 Hz, 3H), 1.15 (s, 3H),
75.9, 113.4, 125.8, 126.8, 127.2, 128.1, 140.3, 148.3, 158.5. IR (neat)
3464, 2974, 1610, 1509, 1446, 1250, 1178, 1029 cmꢂ1. HRMS (FABþ)
calcd for C15H15O [MꢂOH]þ 211.1123, found 211.1128. Chiral HPLC
OJ-H, n-hexane/i-PrOH¼9/1, 1.0 mL/min, tR¼39.8 min (minor, R),
51.2 min (major, S).
1.15e1.70 (m, 8H), 1.49 (q, J¼7.2 Hz, 2H). 13C NMR (100 MHz, CDCl3)
d
8.3, 21.7, 22.7, 26.5, 28.0, 34.3, 39.6, 41.6, 73.1. IR (neat) 3387, 2956,
1464, 1367, 1154 cmꢂ1. HRMS (EIþ) calcd for C10H20 [MꢂH2O]þ
140.1565, found 140.1564. Chiral GC CHIRALDEX B-DM, 75 ꢀC,
tR¼12.2 min (major, S), 13.1 min (minor, R).
4.5.3. (S)-1-(2-Naphthalenyl)-1-phenylethanol (6c)10a
MHz, CDCl3) 1.98 (s, 3H), 2.42 (br, 1H), 7.15e7.48 (m, 8H), 7.66e7.84
(m, 3H), 7.93 (m, 1H). 13C NMR (100 MHz, CDCl3)
30.7, 76.3, 123.7,
125.0, 125.9, 126.0, 126.1, 127.0, 127.5, 127.9, 128.2, 128.3, 132.3, 133.0,
.
1H NMR (400
4.3.11. (S)-2-Cyclohexylbutan-2-ol (3k)19
.
1H NMR (400 MHz, CD
d
Cl3)
d
0.89 (t, J¼7.2 Hz, 3H), 0.90e1.38 (m, 7H), 1.07 (s, 3H), 1.49 (t,
d
J¼7.2 Hz, 2H), 1.62e1.86 (m, 5H). 13C NMR (100 MHz, CDCl3)
d 7.6,
23.4, 26.6, 26.8, 26.9, 27.5, 32.1, 46.7, 74.5. IR (neat) 3420, 2965,
2926, 2853, 1450, 1375, 1142 cmꢂ1. HRMS (EIþ) calcd for C10H18
[MꢂH2O]þ 138.1409, found 138.1411. Chiral GC CHIRALDEX B-DM,
80 ꢀC, tR¼26.9 min (major, S), 28.5 min (minor, R).
145.3, 147.7. IR (neat) 3433, 3056, 1493, 1446, 1373, 1126, 1065 cmꢂ1
.
HRMS (FABþ) calcd for C18H15 [MꢂOH]þ 231.1174, found 231.1174.
Chiral HPLC OD-H, n-hexane/i-PrOH¼20/1, 0.5 mL/min, tR¼34.2 min
(major, S), 39.8 min (minor, R).
4.3.12. (R)-1-Ethyl-1,2,3,4-tetrahydronaphthalen-1-ol (3l)20
(400 MHz, CDCl3)
.
1H NMR
4.5.4. (S)-1-Phenyl-1,2,3,4-tetrahydronaphthalen-1-ol (6d)10a
(400 MHz, CDCl3) 1.78 (m, 1H), 1.90e2.20 (m, 3H), 2.16 (s, 1H),
2.80e2.96 (m, 2H), 7.00e7.40 (m, 9H). 13C NMR (100 MHz, CDCl3)
19.7, 29.9, 41.5, 75.4, 126.4, 126.5, 126.6, 127.5, 127.8, 128.9, 129.0,
.
1H NMR
d
0.89 (t, J¼7.2 Hz, 3H), 1.75e2.15 (m, 4H), 1.71 (s,
d
1H), 1.87 (q, J¼7.2 Hz, 2H), 2.60e2.90 (m, 2H), 7.07 (m, 1H), 7.16 (td,
J¼7.2, 1.8 Hz, 1H), 7.19 (td, J¼7.2, 1.8 Hz, 1H), 7.52 (dd, J¼7.2, 1.8 Hz,
d
1H). 13C NMR (100 MHz, CDCl3)
d
8.6, 19.8, 30.0, 34.9, 35.4, 72.7,
137.7, 142.1, 149.0. IR (neat) 3444, 2936, 1488, 1445, 1324, 1068 cmꢂ1
.
126.3, 127.0, 128.9, 136.9, 142.3. IR (neat) 3445, 2935, 1677, 1455,
HRMS (FABþ) calcd for C16H15 [MꢂOH]þ 207.1174, found 207.1171.
Chiral GC CHIRALDEX B-DM, 160 ꢀC, tR¼18.1 min (minor, R), 19.4 min
(major, S).
1287, 1161 cmꢂ1. HRMS (FABþ) calcd for C12H15 [MꢂOH]þ 159.1174,
found 159.1174. Chiral GC CP-Cyclodextrin-b
-2,3,6-M-19, 140 ꢀC,
tR¼18.0 min (minor, S), 18.8 min (major, R).
4.5.5. (S)-1-(Furan-2-yl)-1-phenylethanol (6e)21. 1H NMR (400 MHz,
4.3.13. (S)-1-Phenylpropan-1-ol (5)10a
.
1H NMR (400 MHz, CDCl3)
CDCl3)
d
1.87 (s, 3H), 2.59 (br, 1H), 6.25 (d, J¼3.3 Hz,1H), 6.33 (m,1H),
d
0.91 (t, J¼7.5 Hz, 3H), 1.69e1.77 (m, 2H), 2.24 (br, 1H), 4.56 (t,
7.19e7.40 (m, 6H). 13C NMR (100 MHz, CDCl3)
d
29.3, 73.1,106.4,110.1,
J¼6.9 Hz, 1H), 7.25e7.38 (m, 5H). 13C NMR (100 MHz, CDCl3)
d
10.2,
125.3, 127.4, 128.3, 142.2, 145.8, 158.9. IR (neat) 3388, 1665, 1594,
1500,1470,1447,1368,1224,1155,1069,1010 cmꢂ1. HRMS (EIþ) calcd
for C12H12O2 [M]þ 188.0837, found 188.0829. Chiral GC CHIRALDEX
B-DM, 120 ꢀC, tR¼14.5 min (minor, R), 15.6 min (major, S).
31.9, 75.9,126.0, 127.5, 128.4, 144.7. IR (neat) 3360, 2963,1492,1454,
1377, 1200, 1097, 1013 cmꢂ1. HRMS (FABþ) calcd for C9H13O [MþH]þ
137.0966, found 137.0964. Chiral GC CP-Cyclodextrin-b-2,3,6-M-19,
115 ꢀC, tR¼13.3 min (minor, R), 13.7 min (major, S).
4.5.6. (S)-1-Phenyl-1-(3-thiophenyl)ethanol (6f)10a 1H NMR (400
.
4.4. General procedure for the catalytic enantioselective
addition of Ph2Zn to ketones
MHz, CDCl3)
d
1.92 (s, 3H), 2.28 (br, 1H), 6.97 (dd, J¼5.1, 1.5 Hz, 1H),
7.17 (dd, J¼3.0, 1.5 Hz, 1H), 7.20e7.36 (m, 4H), 7.38e7.46 (m, 2H). 13C
NMR (100 MHz, CDCl3)
d 31.1, 74.6, 120.8, 125.4, 126.0, 126.7, 127.0,
A well-dried Pyrex Schlenk tube was charged with diphenylzinc
(220 mg, 1.0 mmol) and neat Et2Zn (0.20 mL, 2.0 mmol) at the room
temperature under nitrogen atmosphere. The mixture was stirred
for 30 min, and then 1a (45.6 mg, 0.10 mmol) was added to the
mixture. This solution was stirred for another 30 min, and then
ketone (2) (1.0 mmol) was added. The resulting heterogeneous
solution was stirred at room temperature for 2e16 h. Ether (or n-
128.2, 147.4, 149.7. IR (neat) 3418, 2978, 1492, 1446, 1370, 1231,
1069 cmꢂ1. HRMS (FABþ) calcd for C12H11S [MꢂOH]þ 187.0581, found
187.0584. Chiral GC CHIRALDEX B-DM, 140 ꢀC, tR¼18.3 min (minor,
R), 19.1 min (major, S).
.
4.5.7. (S)-3-Bromo-2,4-diphenylbut-3-en-2-ol (6g)22 1H NMR (400
MHz, CDCl3) 1.91 (s, 3H), 2.76 (br, 1H), 7.29e7.34 (m, 3H), 7.38
d