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2.4.17. (R)-1-Chloro-3-(4-(3-oxobutyl)phenoxy)propan-2-ol
(R)-1i
Colourless liquid; yield 42%; purity 98% (GC); 99% ee
(RT = 23.16 min; hexane/i-PrOH 8:2, 0.6 mL/min); [␣]D = +0.8 (c 1.0,
CHCl3).
119.8 (C4, Ar), 124.1 (C3, Ar), 132.2 (C2, Ar), 134.6 (C5, Ar), 153.9
(C1, Ar); IR, (film), cm−1: 3247, 2962, 2911, 2867, 2834, 1613, 1582,
1506, 1256; MS, m/z (%): 265 (7, M+); 135 (4); 72 (100).
2.5.4. ( )-1-Isopropylamino-3-(4-(3-oxobutyl)phenoxy)propan-2-ol
(
)-4h
Colourless needles; m.p. 61 ◦C (hexane); yield 80%; purity 96%
2.4.18. (S)-1-Chloro-3-(4-(3-oxobutyl)phenoxy)prop-2-yl
acetate (S)-2i
Colourless liquid; yield 45%; purity 98% (GC); 99% ee
(RT = 13.84 min; hexane/i-PrOH 8:2, 0.6 mL/min); [␣]D = +25.6 (c
1.0, CHCl3).
(HPLC); 1H NMR: ı 1.09 (d, 6H, J = 6.3 Hz, CH(CH3)2), 2.13 (s, 1H,
CH3CO), 2.46 (s (br), 1H, OH), 2.68–2.92 (m, 6H, ArCH2CH2, CH2NH),
3.92–4.06 (m, 3H, OCH2CH(OH)), 6.83 (ddd, 2H, J = 8.7 Hz, J = 2.5 Hz,
J = 0.5 Hz, ArH), 7.09 (ddd, 2H, J = 8.7 Hz, J = 2.5 Hz, J = 0.5 Hz, ArH);
13C NMR: ı 22.9 (CH(CH3)2), 28.8 (COCH3), 30.0 (ArCH2CH2),
45.3 (ArCH2CH2), 48.8 (CH2NH or (CH(CH3)2), 49.4 (CH2NH or
(CH(CH3)2), 68.4 (CHOH), 70.6 (CH2OAr), 114.5 (C3, C5, Ar), 129.1
(C3, C5, Ar), 133.2 (C4, Ar), 157.0 (C1, Ar), 208.0 (COCH3); IR, (film),
cm−1: 3275, 2967, 2924, 2866, 2359, 1707, 1613, 1584, 1510, 1221;
MS, m/z (%): 235 (8); 207 (6); 73 (6); 72 (100); 43 (11).
2.5. General procedure for preparation of ( )-1-alkylamino-
3-aryloxypropan-2-ols ( )-4 and ( )-5 from ( )-3
To 3 mmol ( )-2-aryloxymethyloxirane 3 in 9 mL of amine (iso-
propylamine or tert-butylamine) 3 ml of water was added. The
mixture was left at room temperature until disappearance of the
oxirane was indicated by TLC (hexane–ethyl acetate, 6:4). After
∼24 h an excess of amine was evaporated, residue diluted with
saturated NaHCO3 (10 mL) and extracted with CH2Cl2 (3 × 10 mL).
Organic layer was dried over anhydrous MgSO4 and solvent was
evaporated.
2.5.5. ( )-1-tert-Butylamino-3-(2-methoxyphenoxy)propan-2-ol
(
)-5a
White solid, m.p. 73–75 ◦C; yield 95%; purity 94% (HPLC); 1H
NMR: ı 1.11 (s, 9H, C(CH3)3), 2.72 (dd, 1H, J = 11.8 Hz, J = 6.1 Hz,
CH2NH), 2.84 (dd, 1H, J = 11.8 Hz, J = 4.1 Hz, CH2NH), 3.86 (s, 3H,
CH3OAr), 3.93–4.09 (m, 1H, CHOH), 3.96 (dd, 1H, J = 8.8 Hz, J = 4.2 Hz,
CH2OAr), 4.05 (dd, 1H, J = 11.0 Hz, J = 4.8 Hz, CH2OAr), 6.86–6.87 (m,
4H, ArH) 13C NMR: ı 26.9 (C(CH3)3), 45.3 (CH2NH), 55.1 (C(CH3)3),
55.8 (OCH3), 66.2 (CHOH), 72.3 (CH2OAr), 112.0 (C6, Ar), 114.7 (C3,
Ar), 121.0 (C5, Ar), 122.1 (C4, Ar), 147.9 (C1, Ar), 149.6 (C2, Ar); IR,
(film), cm−1: 3297, 3067, 2964, 1592, 1506, 1227; MS, m/z (%): 238
(21); 209 (22); 124 (9); 86 (100); 57 (14).
2.5.1. ( )-1-Isopropylamino-3-(4-ethyl-2-methoxyphenoxy)
-propan-2-ol ( )-4b
Yellow liquid; yield 96%; purity 99% (HPLC); 1H NMR: ı 1.08
(d, 6H, J = 6.2 Hz, CH(CH3)2), 1.21 (t, 3H, J = 7.6 Hz, CH3CH2), 2.58
(q, 2H, J = 7.6 Hz, CH3CH2), 2.70–2.89 (m, 1H, CH(CH3)2), 2.73 (dd,
1H, J = 12.0 Hz, J = 7.1 Hz, CH2NH), 2.86 (dd, 1H, J = 12.0 Hz, J = 4.0 Hz,
CH2NH), 3.25 (s (br), OH), 3.83 (s, 3H, CH3OAr), 3.93–4.11 (m, 3H,
OCH2CH(OH)), 6.70 (d, 1H, J = 8.5 Hz, ArH), 6.71 (s, 1H, ArH), 6.83 (d,
1H, J = 8.0 Hz, ArH); 13C NMR: ı 14.0 (CH3CH2), 21.0 (CH(CH3)2), 26.7
(CH3CH2), 47.1 (CH2NH or (CH(CH3)2), 47.8 (CH2NH or (CH(CH3)2),
54.0 (OCH3), 66.6 (CHOH), 71.5 (CH2OAr), 110.2 (C6, Ar), 113.2 (C3,
Ar), 118.0 (C5, Ar), 136.3 (C4, Ar), 144.5 (C1, Ar), 147.5 (C2, Ar); IR,
(film), cm−1: 3323, 3280, 3127, 2962, 1589, 1515, 1229; MS, m/z
(%): 223 (12); 152 (38); 137 (8); 72 (100).
2.5.6. ( )-1-tert-Butylamino-3-(4-ethyl-2-methoxyphenoxy)-
propan-2-ol ( )-5b
Yellow liquid; yield 96%; purity 99% (HPLC); 1H NMR: ı 1.10 (s,
9H, C(CH3)3), 1.21 (t, 3H, J = 7.6 Hz, CH3CH2), 2.58 (q, 2H, J = 7.6 Hz,
CH3CH2), 2.71 (dd, 1H, J = 11.6 Hz, J = 5.6 Hz, CH2NH), 2.83 (dd, 1H,
J = 11.4 Hz, J = 3.6 Hz, CH2NH), 3.84 (s, 3H, CH3OAr), 3.96–4.03 (m,
3H, OCH2CH(OH)), 6.71 (d, 1H, J = 6.7 Hz, ArH), 6.73 (s, 1H, ArH), 6.85
(d, 1H, J = 8.5 Hz, ArH); 13C NMR: ı 15.7 (CH3CH2), 28.4 (CH3CH2),
28.9 (C(CH3)3), 44.7 (CH2NH), 50.0 (C(CH3)3), 55.7 (OCH3), 68.5
(CHOH), 73.1 (CH2OAr), 111.8 (C6, Ar), 114.7 (C3, Ar), 119.6 (C5,
2.5.2. ( )-1-Isopropylamino-3-(2-nitrophenoxy)propan-2-ol
(
)-4d
Yellow solid; yield 90%; purity 97% (GC); 1H NMR: ı 1.10 (d, 6H,
Ar), 137.8 (C4, Ar), 146.2 (C1, Ar), 149.5 (C2, Ar); IR, (film), cm−1
:
J = 6.2 Hz, CH(CH3)2), 2.68 (s (br), OH), 2.76–2.93 (m, 1H, CH(CH3)2)
2.82 (dd, 1H, J = 12.3 Hz, J = 6.4 Hz, CH2NH), 2.92 (dd, 1H, J = 12.1 Hz,
J = 4.4 Hz, CH2NH), 4.05 (qui, 1H, J = 5.2 Hz CHOH), 4.10–4.20 (m, 2H,
CH2OAr), 7.05 (t, 1H, J = 7.8 Hz, ArH), 7.11 (d, 1H, J = 8.5 Hz, ArH),
7.54 (t, 1H, J = 8.0 Hz, ArH), 7.87 (d, 1H, J = 8.0 Hz, ArH); 13C NMR:
ı 22.8 (CH(CH3)2), 48.8 (CH2NH or (CH(CH3)2), 49.0 (CH2NH or
(CH(CH3)2), 67.9 (CHOH), 72.4 (CH2OAr), 114.8 (C6, Ar), 120.6 (C4,
Ar), 125.7 (C3, Ar), 134.3 (C5, Ar), 139.7 (C2, Ar), 152.3 (C1, Ar);
IR, (film), cm−1: 3265, 3076, 2964, 2943, 2904, 1612, 1582, 1518,
1287; MS, m/z (%): 239 (5); 210 (5); 73 (5); 72 (100); 56 (8); 41
(6).methylphenoxy)propan-
3305, 3118, 2964, 1588, 1514, 1229; MS, m/z (%): 266 (16); 237
(19); 152 (17); 137 (10); 86 (100); 71 (9); 57 (12).
2.5.7. ( )-1-tert-Butylamino-3-(2-nitrophenoxy)propan-2-ol
(
)-5d
Yellow solid; yield 85%; purity 90% (GC); 1H NMR: ı 1.15 (s,
9H, C(CH3)3), 2.81 (dd, 1H, J = 12.0 Hz, J = 6.5 Hz, CH2NH), 2.92 (dd,
1H, J = 12.1 Hz, J = 4.5 Hz, CH2NH), 4.00 (qui, 1H, J = 5.3 Hz, CHOH),
4.12–4.22 (m, 2H, CH2OAr), 7.05 (t, 1H, J = 7.5 Hz, ArH), 7.12 (d, 1H,
J = 8.0 Hz, ArH), 7.54 (t, 1H, J = 7.5 Hz, ArH), 7.88 (d, 1H, J = 8.0 Hz,
ArH); 13C NMR: ı 28.9 (C(CH3)3), 44.3 (CH2NH), 50.2 (C(CH3)3), 68.0
(CHOH), 72.4 (CH2OAr), 114.7 (C6, Ar), 120.5 (C4, Ar), 125.6 (C3, Ar),
134.2 (C5, Ar), 139.6 (C2, Ar), 152.3 (C1, Ar); IR, (film), cm−1: 3289,
3094, 2959, 2867, 1609, 1581, 1520, 1259; MS, m/z (%): 253 (37);
224 (6); 86 (100); 71 (8); 70 (14); 57 (21); 41 (10).
2.5.3. ( )-1-Isopropylamino-3-(2-isopropyl-5-methylphenoxy)-
propan-2-ol ( )-4f
Yellow liquid; yield 93%; purity 99% (GC); 1H NMR: ı 1.08 (d,
6H, J = 6.2 Hz, CH(CH3)2), 1.20 (d, 6H, J = 6.9 Hz, (CH3)2CH), 2.30 (s,
3H, CH3Ar), 2.75 (dd, 1H, J = 12.0 Hz, J = 7.4 Hz, CH2NH), 2.80 (sp,
1H, J = 6.2 Hz, CH(CH3)2), 2.91 (dd, 1H, J = 12.1 Hz, J = 3.8 Hz, CH2NH),
3.27 (sp, 1H, J = 6.9 Hz, (CH3)2CH)), 3.92 (dd, 1H, J = 9.1 Hz, J = 5.4 Hz,
CH2OAr), 4.00 (dd, 1H, J = 9.1 Hz, J = 5.0 Hz, CH2OAr), 4.02–4.10 (m,
1H, CHOH), 6.67 (s (br), 1H, ArH), 6.74 (d, 1H, J = 7.7 Hz, ArH), 7.08
(d, 1H, J = 7.7 Hz, ArH); 13C NMR: ı 19.6 (CH3Ar), 21.0 ((CH3)2CH),
21.3 (CH(CH3)2), 24.9 ((CH3)2CH), 47.2 (CH2NH or (CH(CH3)2), 48.0
(CH2NH or (CH(CH3)2), 66.8 (CHOH), 69.0 (CH2OAr), 110.7 (C6, Ar),
2.5.8. ( )-1-tert-Butylamino-3-(2-isopropyl-5-methylphenoxy)-
propan-2-ol ( )-5f
Yellow liquid; yield 90%; purity 99.2% (GC); 1H NMR: ı 1.18 (s,
9H, C(CH3)3), 1.27 (d, 6H, J = 6.9 Hz, (CH3)2CH), 2.37 (s, 3H, CH3Ar),
2.80 (dd, 1H, J = 11.8 Hz, J = 6.9 Hz CH2NH), 2.95 (dd, 1H, J = 11.8 Hz,
J = 3.8 Hz, CH2NH), 3.33 (sp, 1H, J = 6.9 Hz, (CH3)2CH), 3.96–4.11 (m,
3H, OCH2CH(OH)), 6.74 (s, 1H, ArH), 6.81 (d, 1H, J = 7.5 Hz, ArH), 7.14
(d, 1H, J = 7.7 Hz, ArH); 13C NMR: ı 19.6 (CH3Ar), 21.0 ((CH3)2CH),