792
E. Fernández-Mateos et al. / Tetrahedron: Asymmetry 23 (2012) 789–794
5.09 (q, J = 6.4 Hz, 1H), 2.32 (s, 3H), 1.99 (br s, 1H), 1.44 (d,
J = 6.4 Hz, 3H). 13C NMR (75 MHz, CDCl3) d 143.8, 134.1, 130.3,
127.1, 126.3, 124.4, 66.7, 23.9, 18.9. LRMS (EI) m/z: 136 (M+, 2),
121 (16), 119 (10), 118 (80), 117 (100), 115 (44), 103 (10), 93
(16), 91 (44), 77 (15), 65 (12), 63 (11). Ee determination by chiral
GC analysis, HP-CHIRAL-20b column, T = 120 °C, P = 14.3 psi, reten-
tion times: tr(R) = 24.2 min, tr(S) = 27.2 min (major enantiomer).
4.86 (q, J = 6.5 Hz, 1H), 2.40 (br s, 1H), 1.46 (d, J = 6.5 Hz, 3H). 13C
NMR (101 MHz, CDCl3) d 144.2, 133.0, 128.5, 126.8, 69.7, 25.2.
LRMS (EI) m/z: 156 (M+, 11), 143 (13), 141 (46), 140 (34), 139
(23), 138 (100), 113 (14), 112 (13), 103 (72), 102 (22), 101 (12),
77 (60), 75 (22), 74 (12), 51 (23), 50 (14). Ee determination by chi-
ral GC analysis, HP-CHIRAL-20b column, T = 125 °C, P = 14.3 psi,
retention
times:
tr(R) = 35.6 min,
tr(S) = 37.6 min
(major
enantiomer).
4.2.3. (S)-1-(m-Tolyl)ethanol 2c13
Compound 2c was obtained after purification by Kugelrohr dis-
4.2.8. (S)-4-(1-Hydroxyethyl)benzonitrile 2h17
tillation as a colorless oil (98% yield, 94% ee); ½a D20
ꢃ
¼ ꢁ51:0 (c 1.0,
Compound 2h was obtained after purification by Kugelrohr dis-
CHCl3) {Lit.13
½
a 1D6
ꢃ
¼ ꢁ47:3 (c 0.8, CHCl3) for 90% ee}. 1H NMR
tillation as a colorless oil (99% yield, 94% ee); ½a D20
¼ ꢁ49:0 (c 1.0,
ꢃ
(300 MHz, CDCl3) d 7.23 (dd, J = 7.2, 3.7 Hz, 1H), 7.20–7.13 (m,
2H), 7.08 (d, J = 7.3 Hz, 1H), 4.85 (q, J = 6.4 Hz, 1H), 2.36 (s, 3H),
1.92 (br s, 1H), 1.48 (d, J = 6.5 Hz, 3H). 13C NMR (75 MHz, CDCl3)
d 145.8, 138.1, 128.4, 128.2, 126.1, 122.4, 70.4, 25.1, 21.4. LRMS
(EI) m/z: 136 (M+, 11), 121 (23), 119 (16), 118 (93), 117 (100),
115 (40), 103 (13), 93 (27), 92 (11), 91 (53), 77 (17), 65 (13), 51
(9). Ee determination by chiral GC analysis, HP-CHIRAL-20b col-
umn, T = 120 °C, P = 14.3 psi, retention times: tr(R) = 20.1 min,
tr(S) = 20.6 min (major enantiomer).
CHCl3) {Lit.17
½
a 2D0
ꢃ
¼ ꢁ62:7 (c 2.1, CHCl3) for 72% ee}. 1H NMR
(300 MHz, CDCl3) d 7.63 (d, J = 8.3 Hz, 2H), 7.49 (d, J = 8.1 Hz, 2H),
4.96 (q, J = 6.5 Hz, 1H), 2.22 (br s, 1H), 1.49 (d, J = 6.5 Hz, 3H). 13C
NMR (75 MHz, CDCl3) d 151.1, 132.3, 126.0, 118.8, 111.0, 69.6,
25.4. LRMS (EI) m/z: 147 (M+, 8), 132 (100), 130 (25), 129 (53),
128 (17), 104 (85), 103 (19), 102 (32), 77 (27), 76 (16), 75 (14),
51 (13). Ee determination by chiral GC analysis, HP-CHIRAL-20b
column, T = 150 °C, P = 14.3 psi, retention times: tr(R) = 42.6 min,
tr(S) = 45.1 min (major enantiomer).
4.2.4. (S)-1-(p-Tolyl)ethanol 2d14
4.2.9. (S)-1-[4-(1-Hydroxyethyl)phenyl]ethanone 2i18
Compound 2d was obtained after purification by Kugelrohr dis-
Compound 2i was obtained after purification by Kugelrohr dis-
tillation as a colorless oil (99% yield, 94% ee); ½a D20
ꢃ
¼ ꢁ54:5 (c 1.0,
tillation as a colorless oil (99% yield, 94% ee); ½a D20
¼ ꢁ42:6 (c 1.0,
ꢃ
CHCl3) {Lit.14
½
a 2D0
ꢃ
¼ ꢁ53:7 (c 0.4, CHCl3) for 96% ee}. 1H NMR
CHCl3) {Lit.18
½
a 2D5
ꢃ
¼ ꢁ44:9 (c 1.2, CHCl3) for 98% ee}. 1H NMR
(400 MHz, CDCl3) d 7.26 (d, J = 8.2 Hz, 2H), 7.15 (d, J = 7.6 Hz, 2H),
4.86 (q, J = 6.4 Hz, 1H), 2.34 (s, 3H), 2.03 (br s, 1H), 1.48 (d,
J = 6.5 Hz, 3H). 13C NMR (101 MHz, CDCl3) d 142.8, 137.1, 129.1,
125.3, 70.2, 25.0, 21.1. LRMS (EI) m/z: 136 (M+, 9), 121 (27), 119
(13), 118 (84), 117 (100), 115 (38), 103 (11), 93 (19), 91 (48), 77
(15), 65 (12). Ee determination by chiral GC analysis, HP-CHIRAL-
20b column, T = 120 °C, P = 14.3 psi, retention times:
tr(R) = 19.3 min, tr(S) = 20.1 min (major enantiomer).
(300 MHz, CDCl3) d 7.88 (d, J = 8.3 Hz, 2H), 7.42 (d, J = 8.4 Hz, 2H),
4.92 (q, J = 6.5 Hz, 1H), 2.61 (br s, 1H), 2.55 (s, 3H), 1.47 (d,
J = 6.5 Hz, 3H).13C NMR (75 MHz, CDCl3) d 198.0, 151.3, 136.1,
128.5, 125.4, 69.7, 26.5, 25.2. LRMS (EI) m/z: 164 (M+, 6), 150
(10), 149 (97), 122 (10), 121 (100), 106 (8), 105 (10), 103 (18),
91 (10), 78 (9), 77 (30), 51 (13). Ee determination by chiral GC anal-
ysis, CP-Chiralsil-DEX CB column, T = 150 °C, P = 14.3 psi, retention
times: tr(R) = 20.0 min, tr(S) = 20.6 min (major enantiomer).
4.2.5. (S)-1-(4-Methoxyphenyl)ethanol 2e15
4.2.10. (S)-1-(Naphthalen-2-yl)ethanol 2j14
Compound 2e was obtained after purification by Kugelrohr dis-
Compound 2j was obtained after purification by Kugelrohr dis-
tillation as a white powder (99% yield, 94% ee); mp 56–58 °C,
tillation as a colorless oil (87% yield, 94% ee); ½a D20
¼ ꢁ44:0 (c 1.0,
ꢃ
CHCl3) {Lit.15
½
a 2D0
ꢃ
¼ ꢁ51:9 (c 1.0, CHCl3) for 97% ee}. 1H NMR
½
a 2D0
ꢃ
¼ ꢁ46:0 (c 1.0, CHCl3) {Lit.14
½
a 2D0
ꢃ
¼ ꢁ48:1 (c 1.5, CHCl3) for
(300 MHz, CDCl3) d 7.30 (d, J = 8.7 Hz, 2H), 6.88 (d, J = 8.7 Hz, 2H),
4.85 (q, J = 6.4 Hz, 1H), 3.80 (s, 3H), 1.85 (br s, 1H), 1.47 (d,
J = 6.4 Hz, 3H). 13C NMR (75 MHz, CDCl3) d 159.0, 138.0, 126.6,
113.8, 70.0, 55.3, 25.0. LRMS (EI) m/z: 152 (M+, 6), 137 (23), 135
(14), 134 (100), 119 (50), 109 (9), 91 (54), 77 (12), 65 (23), 63
(10), 51 (6). Ee determination by chiral GC analysis, HP-CHIRAL-
20b column, T = 120 °C, P = 14.3 psi, retention times:
tr(R) = 53.5 min, tr(S) = 54.9 min (major enantiomer).
92% ee}. 1H NMR (300 MHz, CDCl3) d 7.84–7.70 (m, 4H), 7.50–
7.39 (m, 3H), 4.98 (q, J = 6.4 Hz, 1H), 2.39 (br s, 1H), 1.52 (d,
J = 6.5 Hz, 3H). 13C NMR (75 MHz, CDCl3) d 143.1, 133.2, 132.8,
128.2, 127.9, 127.6, 126.0, 125.7, 123.8, 123.7, 70.4, 25.0. LRMS
(EI) m/z: 172 (M+, 6), 155 (16), 154 (100), 153 (56), 152 (37), 151
(12), 129 (27), 128 (18), 127 (12), 76 (18), 63 (6). Ee determination
by chiral GC analysis, HP-CHIRAL-20b column, T = 150 °C, P = 14.3
psi, retention times: tr(R) = 66.1 min, tr(S) = 67.5 min (major
enantiomer).
4.2.6. (S)-1-(4-(Trifluoromethyl)phenyl)ethanol 2f11
Compound 2f was obtained after purification by Kugelrohr dis-
4.2.11. (S)-1-(Thiophen-2-yl)ethanol 2k14
tillation as a colorless oil (100% yield, 94% ee); ½a D20
ꢃ
¼ ꢁ37:0 (c 1.0,
Compound 2k was obtained after purification by Kugelrohr dis-
CHCl3) {Lit.11
½
a 2D0
ꢃ
¼ ꢁ33:7 (c 5.5, CHCl3) for 97% ee}. 1H NMR
tillation as a colorless oil (68% yield, 80% ee); ½a D20
¼ ꢁ30:0 (c 1.0,
ꢃ
(300 MHz, CDCl3) d 7.60 (d, J = 8.2 Hz, 2H), 7.47 (d, J = 8.6 Hz, 2H),
4.95 (q, J = 6.5 Hz, 1H), 2.16 (br s, 1H), 1.49 (d, J = 6.5 Hz, 3H). 13C
NMR (75 MHz, CDCl3) d 149.7, 129.8, 129.4, 125.6, 125.4, 125.4,
122.3, 69.8, 25.3. LRMS (EI) m/z: 190 (M+, 7), 175 (100), 173 (18),
172 (40), 171 (14), 151 (13), 145 (22), 127 (93), 103 (16), 77
(12). Ee determination by chiral GC analysis, HP-CHIRAL-20b col-
umn, T = 130 °C, P = 14.3 psi, retention times: tr(R) = 11.1 min,
tr(S) = 11.7 min (major enantiomer).
CHCl3) {Lit.14
½
a 2D0
ꢃ
¼ ꢁ27:6 (c 1.0, CHCl3) for 94% ee}. 1H NMR
(400 MHz, CDCl3) d 7.24 (dd, J = 4.8, 1.4 Hz, 1H), 7.00–6.94 (m,
2H), 5.13 (q, J = 6.4 Hz, 1H), 2.09 (br s, 1H), 1.60 (d, J = 6.4 Hz,
3H). 13C NMR (101 MHz, CDCl3) d 149.83, 126.62, 124.40, 123.15,
66.22, 25.23. LRMS (EI) m/z: 128 (M+, 11), 113 (22), 111 (18), 110
(100), 109 (43), 85 (32), 84 (26), 66 (24), 65 (10), 58 (10). Ee deter-
mination by chiral GC analysis, HP-CHIRAL-20b column, T = 120 °C,
P = 14.3 psi, retention times: tr(R) = 14.3 min, tr(S) = 15.0 min (ma-
jor enantiomer).
4.2.7. (S)-1-(4-Chlorophenyl)ethanol 2g16
Compound 2g was obtained after purification by Kugelrohr dis-
4.2.12. (S)-1-(Furan-2-yl)ethanol 2l14
tillation as a colorless oil (92% yield, 94% ee); ½a D20
ꢃ
¼ ꢁ43:0 (c 1.0,
Compound 2l was obtained after purification by Kugelrohr dis-
CHCl3) {Lit.16
½
a 2D0
ꢃ
¼ ꢁ43:6 (c 1.0, CHCl3) for 97% ee}. 1H NMR
tillation as a colorless oil (75% yield, 88% ee); ½a D20
¼ ꢁ22:6 (c 1.0,
ꢃ
(400 MHz, CDCl3) d 7.31 (d, J = 9.0 Hz, 2H), 7.28 (d, J = 8.9 Hz, 2H),
CHCl3) {Lit.14
½
a 2D0
ꢃ
¼ ꢁ19:8 (c 0.9, CHCl3) for 98% ee}. 1H NMR