Tethered Aminohydroxylation
1258 (w), 1041 cmꢀ1 (m); HRMS (ESI): m/z calcd for C8H15NNaO4:
212.0893; found: 212.0893 (0.04 ppm).
(s), 1742 (s), 1520 (m), 1433 (m), 1267 (m), 1065 (m), 1026 cmꢀ1 (s);
HRMS (ESI): m/z calcd for C15H21NNaO4: 302.1363; found: 302.1364
(0.4 ppm).
(ꢂ)(R)-4-[(1’R,2’R)-1’,2’-Dihydroxypentyl]oxazolidin-2-one (anti-9h)
(ꢂ)(R)-4-{(1’R,2’R)-[2’-(Benzyloxy)-1’-hydroxy-2’-
methylbutyl]}oxazolidin-2-one (syn-19b)
1H NMR (400 MHz, CD3OD): d=0.98 (t, J=7.3 Hz, 3H), 1.34–1.64 (m,
4H), 3.46 (dd, J=5.7, 2.2 Hz, 1H), 3.56 (ddd, J=7.9, 5.0, 2.2 Hz, 1H),
4.01 (appdt, J=8.8, 5.7 Hz, 1H), 4.46 (appt, J=8.8 Hz, 1H), 4.52 ppm
(dd, J=8.8, 6.0 Hz, 1H); 13C NMR (100 MHz, CD3OD): d=14.4, 20.1,
36.8, 56.0, 68.6, 72.2, 75.2, 162.6 ppm; IR (thin film): n˜max =3375 (brs),
2921 (s), 1738 (s), 1416 (w), 1258 (m), 1041 cmꢀ1 (m); HRMS (ESI): m/z
calcd for C8H15NNaO4: 212.0893; found: 212.0894 (ꢀ0.3 ppm).
1H NMR (400 MHz, CD3OD): d=1.02 (d, J=6.8 Hz, 3H), 1.07 (d, J=
6.8 Hz, 3H), 2.04–2.18 (m, 1H), 3.21 (dd, J=7.2, 2.4 Hz, 1H), 3.70 (dd,
J=5.6, 2.3 Hz, 1H), 3.98 (dt, J=8.8, 5.6 Hz, 1H), 4.37 (appt, J=8.8 Hz,
1H), 4.49 (dd, J=8.8, 5.8 Hz, 1H), 4.58 (d, J=11.3 Hz, 1H), 4.69 (d, J=
11.3 Hz, 1H), 7.25–7.43 ppm (m, 5H); 13C NMR (100 MHz, CD3OD):
d=18.4, 18.5, 30.0, 55.2, 67.5, 72.5, 74.2, 84.8, 127.7, 128.0, 128.4, 139.1,
161.6 ppm; IR (thin film): n˜max =3248 (brs), 2956 (s), 2886 (s), 1745 (s),
1260 (m), 1069 cmꢀ1 (m); HRMS (ESI): m/z calcd for C15H21NNaO4:
302.1363; found: 302.1363 (0.1 ppm).
Diastereomeric Mixture of Major Isomer anti-17a with Minor Isomer syn-
17a
1
Data are given for the major isomer. M.p. 88–918C; H NMR (400 MHz,
CD3OD): d=0.96 (t, J=7.3 Hz, 3H), 1.34–1.57 (m, 2H), 1.58–1.79 (m,
2H), 3.40–3.51 (m, 2H), 4.10 (ddd, J=9.0, 6.1, 4.0 Hz, 1H), 4.24 (dd, J=
9.0, 6.1 Hz, 1H), 4.43 (appt, J=9.0 Hz, 1H), 4.52 (d, J=11.4 Hz, 1H),
4.61 (d, J=11.4 Hz, 1H), 7.25–7.40 ppm (m, 5H); 13C NMR (100 MHz,
CD3OD): d=14.7, 18.4, 33.4, 55.8, 69.3, 73.0, 74.0, 81.3, 128.8, 129.1,
129.4, 139.9, 162.8 ppm; IR (KBr disk): n˜max =3343 (brm), 2925 (s), 1747
(s), 1415 (m), 1259 (m), 1093 cmꢀ1 (s); HRMS (ESI): m/z calcd for
C15H21NNaO4: 279.1477; found: 279.1471 (2.3 ppm).
Diastereomeric Mixture of Major Isomer anti-19c and Minor Isomer syn-
19c
Data are given for the major isomer. 1H NMR (400 MHz, CDCl3): d=
1.98–2.38 (brs, 1H), 3.77 (t, J=6.3 Hz, 1H), 3.95 (ddd, J=7.8, 6.3,
6.1 Hz, 1H), 4.22 (d, J=11.6 Hz, 1H), 4.30 (dd, J=9.3, 7.8 Hz, 1H),
4.26–4.31 (m, 1H), 4.40 (dd, J=9.3, 6.1 Hz, 1H), 4.51 (d, J=11.6 Hz,
1H), 5.68 (brs, 1H), 7.20–7.53 ppm (m, 10H); 13C NMR (100 MHz,
CDCl3): d=54.0, 66.2, 70.8, 74.6, 82.2, 127.5, 127.7, 128.1, 128.6, 128.8,
128.9, 137.4, 137.9, 160.5 ppm; IR (thin film): n˜max =3385 (brs), 2875 (s),
2796 (s), 1737 (s), 1512 (m), 1430 (w), 1256 (w), 977 cmꢀ1 (s); HRMS
(ESI): m/z calcd for C18H19NNaO4: 336.1206; found: 336.1210
(ꢀ1.1 ppm).
Diastereomeric Mixture of Major Isomer anti-17b with Minor Isomer syn-
17b
Data are given for the major isomer. 1H NMR (400 MHz, CD3OD): d=
1.00 (d, J=7.0 Hz, 3H), 1.08 (d, J=7.0 Hz, 3H), 2.20–2.12 (m, 1H), J=
7.0, 3.3 Hz, 1H), 3.30–3.37 (m, 1H), 3.47 (dd, J=8.3, 3.8 Hz, 1H), 4.08
(ddd, J=8.8, 5.9, 3.8 Hz, 1H), 4.22 (dd, J=8.8, 5.9 Hz, 1H), 4.38 (appt,
J=8.8 Hz, 1H), 4.62 (d, J=11.1 Hz, 1H), 4.65 (d, J=11.1 Hz, 1H), 7.24–
7.44 ppm (m, 5H); 13C NMR (100 MHz, CD3OD): d=15.9, 19.3, 29.6,
54.9, 68.4, 72.2, 74.8, 85.4, 127.8, 127.9, 128.4, 138.9, 161.8 ppm; IR (thin
film): n˜max =3385 (brs), 2957 (m), 1741 (s), 1634 (m), 1463 (m), 1393 (m),
1190 (m), 1026 cmꢀ1 (m); HRMS (ESI): m/z calcd for C15H21NNaO4:
302.1363; found: 302.1363 (0.0 ppm).
Diastereomeric Mixture of Major Isomer anti-19d with Minor Isomer syn-
19d
Data are given for the major isomer. 1H NMR (400 MHz, CD3OD): d=
1.02 (s, 9H), 3.24 (d, J=3.4 Hz, 1H), 3.89 (t, J=3.6 Hz, 1H), 4.12 (ddd,
J=9.1, 6.1, 3.5 Hz, 1H), 4.28 (t, J=9.1 Hz, 1H), 4.51 (dd, J=9.1, 6.1 Hz,
1H), 4.63 (d, J=11.1 Hz, 1H), 4.66 (d, J=11.1 Hz, 1H), 7.23–7.45 ppm
(m, 5H); 13C NMR (100 MHz, CD3OD): d=26.1, 35.7, 55.1, 66.8, 72.5,
76.2, 91.0, 127.7, 127.8, 128.4, 138.7, 161.5 ppm; IR (thin film): n˜max =3383
(brm), 2956 (m), 1742 (s), 1396 (m), 1246 cmꢀ1 (m); HRMS (ESI): m/z
calcd for C16H23NNaO4: 316.1526; found: 316.1519 (ꢀ2.2 ppm).
Diastereomeric Mixture of Major Isomer anti-17c with Minor Isomer syn-
17c
Data are given for the major isomer. M.p. 161–1648C; 1H NMR
(400 MHz, CDCl3): d=1.96 (brs, 1H), 3.47–3.53 (m, 1H), 3.65–3.75 (m,
1H), 3.92–4.12 (m, 1H), 4.17–4.37 (m, 2H), 4.43–4.55 (m, 2H), 6.53 (s,
1H), 7.20–7.50 ppm (m, 10H); 13C NMR (100 MHz, CDCl3): d=53.8,
67.1, 70.7, 75.9, 82.1, 127.3, 127.6, 128.1, 128.2, 128.6, 129.0, 137.3, 137.7,
160.2 ppm; IR (KBr disk): n˜max =3423 (brs), 2975 (m), 1736 (s), 1637 (m),
1535 (m), 1401 (m), 1203 (m), 978 cmꢀ1 (s); HRMS (ESI): m/z calcd for
C18H19NNaO4: 336.1206; found: 336.1211 (ꢀ1.5 ppm).
(ꢂ)(R)-4-{(2’R,3’R)-[3’-(Benzyloxy)-2’-hydroxyhexan-2-yl]}oxazolidin-2-
one (anti-(Z)-26)
1H NMR (400 MHz, CD3OD): d=0.96 (t, J=7.1 Hz, 3H), 1.18 (s, 3H),
1.28–1.76 (m, 4H), 3.27–3.43 (m, 1H), 3.98 (dd, J=9.1, 6.1 Hz, 1H), 4.22
(dd, J=9.1, 8.8 Hz, 1H), 4.51 (dd, 1H), 4.63 (m, 2H), 7.25–7.43 ppm (m,
5H); 13C NMR (100 MHz, CD3OD): d=14.8, 20.0, 21.7, 34.2, 59.3, 67.6,
75.2, 75.6, 85.2, 128.8, 129.2, 129.5, 139.9, 162.8 ppm; IR (thin film):
n˜max =3415 (brs), 2958 (s), 1747 (s), 1454 (s), 1410 (m), 1248 (m), 1108
(m), 942 cmꢀ1 (w); HRMS (ESI): m/z calcd for C16H23NNaO4: 316.1516;
found: 316.1519 (1.0 ppm).
(ꢂ)(R)-4-{(1’S,2’R)-[2’-(Benzyloxy)-1’-hydroxy-3’,3’-
dimethylbutyl]}oxazolidin-2-one (anti-17d)
1H NMR (400 MHz, CD3OD): d=1.04 (s, 9H), 3.18 (d, J=6.7 Hz, 1H),
3.64 (appt, J=6.7 Hz, 1H), 4.05 (ddd, J=8.8, 6.7, 6.3 Hz, 1H), 4.11 (dd,
J=8.8, 6.3 Hz, 1H), 4.29 (appt, J=8.8 Hz, 1H), 4.66 (s, 2H), 7.27–
7.40 ppm (m, 5H); 13C NMR (100 MHz, CD3OD): d=26.0, 35.7, 56.0,
68.6, 74.1, 76.3, 90.2, 127.7, 127.8, 128.5, 138.6, 161.5 ppm; IR (thin film):
n˜max =3356 (brs), 2957 (s), 1743 (s), 1396 (m), 1246 (m), 1067 (m), 939
(m), 698 cmꢀ1 (m); HRMS (ESI): m/z calcd for C16H23NNaO4: 316.1519;
found: 316.1523 (ꢀ1.2 ppm).
(ꢂ)(R)-4-{(2’R,3’S)-[3’-(Benzyloxy)-2’-hydroxyhexan-2-yl]}oxazolidin-2-
one (syn-(Z)-26)
1H NMR (400 MHz, CD3OD): d=0.94–1.00 (J=7.3 Hz, 3H), 1.18 (s,
3H), 1.33–1.72 (m, 4H), 3.35 (dd, J=7.8, 3.0 Hz, 1H), 4.08 (dd, J=9.1,
5.3 Hz, 1H), 4.36 (appt, J=9.1 Hz, 1H), 4.51 (dd, J=9.1, 5.3 Hz, 1H),
4.64 (d, J=11.8 Hz, 1H), 4.67 (d, J=11.8 Hz, 1H), 7.23–7.43 ppm (m,
5H); 13C NMR (100 MHz, CD3OD): d=13.7, 18.6, 20.2, 32.6, 57.0, 66.7,
74.3, 75.3, 84.0, 127.7, 128.0, 128.4, 138.9, 161.6 ppm; IR (thin film):
n˜max =3414 (brs), 2959 (s), 2872 (s), 1748 (s), 1454 (m), 1409 (s), 1248 (s),
1108 (s), 986 (s), 942 (m), 736 cmꢀ1 (s); HRMS (ESI): m/z calcd for
C16H23NNaO4: 316.1516; found: 316.1519 (1.0 ppm).
(ꢂ)(R)-4-{(1’R,2’S)-[2’-(Benzyloxy)-1’-hydroxy-2’-
methylbutyl]}oxazolidin-2-one (anti-19b)
1H NMR (400 MHz): d=1.00 (d, J=6.8 Hz, 3H), 1.03 (d, J=6.8 Hz,
3H), 2.10–1.90 (m, 1H), J=6.8, 5.9 Hz, 1H), 3.23 (t, J=5.9 Hz, 1H), 3.76
(dd, J=5.9, 2.5 Hz, 1H), 4.06 (ddd, J=9.0, 6.2, 2.5 Hz, 1H), 4.20 (t, J=
9.0 Hz, 1H), 4.47 (dd, J=9.0, 6.1 Hz, 1H), 4.57 (d, J=11.4 Hz, 1H), 4.61
(d, J=11.4 Hz, 1H), 7.24–7.39 ppm (m, 5H); 13C NMR (100 MHz,
CD3OD): d=17.1, 19.0, 30.1, 54.3, 66.1, 71.5, 74.7, 85.8, 127.8, 128.2,
128.5, 138.8, 161.7 ppm; IR (thin film): n˜max =3251 (brs), 2975 (s), 2870
Diastereomeric Mixture of Major Isomer anti-(E)-26 with Minor Isomer
syn-(E)-26
Data are given for the major isomer. 1H NMR (400 MHz, CD3OD): d=
0.99 (t, J=7.1 Hz, 3H), 1.07 (s, 3H), 1.39–1.83 (m, 4H), 3.41 (dd, J=7.8,
3.3 Hz, 1H), 4.08 (dd, J=9.1, 7.1 Hz, 1H), 4.33–4.40 (m, 2H), 4.63 (m,
Chem. Asian J. 2011, 6, 3214 – 3222
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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