1190
Chaudhary et al.:
(CDCl3, 600 MHz): 6.74 (d, J = 8.2, 1 H), 6.67 (d, J = 8.2, 1 H), 4.66 (s, 1 H), 3.93 (s, 3 H),
3.48–3.52 (m , 1 H), 2.85–2.95 (m , 2 H), 2.79 (d, J = 18.5, 1 H), 2.71–2.77 (m , 1 H), 2.55 (dt, J =
12.6, 3.2, 1 H), 2.45 (dt, J = 13.8, 4.6, 1 H), 2.40 (td, J = 13.8, 4.6, 1 H), 1.97 (td, J = 12.3, 4.8,
1 H), 1.82–1.91 (m , 2 H), 1.22 (qd, J = 13.3, 3.2, 1 H). 13C NMR (CDCl3, 150 MHz): 207.6, 145.5,
142.9, 127.3, 126.3, 119.9, 114.7, 91.6, 56.8, 52.4, 47.7, 43.0, 40.3, 39.0, 36.0, 30.8, 25.8. MS (EI),
m/z (%): 285 (9), 87 (11), 86 (21), 85 (65), 84 (35), 83 (100), 49 (14), 48 (13), 47 (33). HRMS
(EI): for C17H19NO3 calculated 285.1365, foun d 285.1364.
Dihydrocodeine (17) and epidihydrocodeine (18). A m ixture of alcoh ols 17 an d 18 (5:4) was
isolated followin g th e protocol for biotran sform ation s usin g Curvularia lunata (ATCC 12017)
in 40% com bin ed yield as colorless oil. Careful purification by flash -colum n ch rom atography
(CHCl3/MeOH) allowed for the preparation of analytically pure sam ples. Data for dihydrocodeine
(17) m atch ed th ose publish ed in th e literature28. RF 0.55 (DCM/MeOH/NH4OH, 98:2:1) (lit.29
21
[α]D –210 (c 0.246, 1,4-dioxan e)). 1H NMR (CDCl3, 600 MHz): 6.74 (d, J = 8.1, 1 H), 6.65
(d, J = 8.2, 1 H), 4.62 (d, J = 5.7, 1 H), 4.03–4.08 (m , 1 H), 3.89 (s, 3 H), 3.08–3.12 (m , 1 H),
3.02 (d, J = 18.3, 1 H), 2.53 (dd, J = 12.0, 4.6, 1 H), 2.36–2.44 (m , 4 H), 2.20–2.29 (m , 2 H),
1.90 (td, J = 12.3, 5.0, 1 H), 1.69–1.75 (m , 1 H), 1.55–1.62 (m , 1 H) 1.41–1.53 (m , 2 H),
1.10–1.19 (m , 1 H). 13C NMR (CDCl3, 150 MHz): 146.2, 141.6, 130.4, 127.0, 119.2, 113.1,
90.5, 67.2, 59.7, 56.4, 46.8, 43.0, 42.2, 40.7, 37.5, 27.2, 20.0, 19.2. MS (EI), m/z (%): 302
(20), 301 (100), 300 (23), 299 (32), 244 (14), 243 (11), 242 (19), 185 (12), 164 (16), 115 (10),
70 (19), 59 (24), 44 (23). HRMS (EI): for C18H23NO3 calculated 301.1678, foun d 301.1678.
Data for epidih ydrocodein e (18) m atch ed th ose publish ed in th e literature28,30. RF 0.51
28
(DCM/MeOH/NH4OH, 98:2:1) (lit.30a [α]D –132 (c 0.32, CHCl3)). 1H NMR (CDCl3, 600 MHz):
6.73 (d, J = 8.2, 1 H), 6.65 (d, J = 8.2, 1 H), 4.37 (d, J = 6.5, 1 H), 3.89 (s, 3 H), 3.43–3.50 (m ,
1 H), 3.09 (m , 1 H), 3.03 (d, J = 18.3, 1 H), 2.53 (dd, J = 11.9, 4.5, 1 H), 2.42 (s, 3 H), 2.36
(dd, J = 18.3, 5.3, 1 H), 2.12–1.23 (m , 2 H), 1.80–1.90 (m , 2 H), 1.69–1.74 (m , 1 H),
1.56–1.63 (m , 1 H), 1.38 (q, J = 12.9, 1 H), 1.00 (q, J = 12.9, 1 H). 13C NMR (CDCl3, 150 MHz):
144.1, 143.5, 130.5, 126.7, 119.0, 113.3, 97.2, 73.3, 59.4, 56.5, 47.0, 43.2, 43.0, 42.9, 35.6,
30.0, 23.7, 20.1. MS (EI), m/z (%): 302 (20), 301 (100), 300 (20), 299 (16), 286 (11), 244 (26),
242 (12), 185 (12), 86 (50), 84 (73), 70 (21), 59 (31), 57 (32), 56 (21), 55 (11), 49 (12), 47 (14),
44 (23). HRMS (EI): for C18H23NO3 calculated 301.1678, foun d 301.1672.
Noroxycodone (19). Th e title com poun d was isolated followin g th e protocol for
biotran sform ation s usin g Cunninghamella echinulata (ATCC 9244) in 15% yield as colorless
oil in 80% purity. Data for 19 m atch ed closely to th ose publish ed in th e literature31. RF 0.21
20
20
(DCM/MeOH/NH4OH, 98:2:1); [α]D –102.7 (c 0.875, MeOH) (lit.31a [α]D –232 (c 0.2);
25
lit.24 (+)-n oroxycodon e: [α]D +100.4 (c 0.55, MeOH)). IR (film ): 3399, 3350, 3007, 2932,
2838, 1725, 1636, 1608, 1505, 1440, 1277, 1051. 1H NMR (CDCl3, 600 MHz): 6.73 (d, J =
8.2, 1 H), 6.66 (d, J = 8.2, 1 H), 4.68 (s, 1 H), 3.92 (s, 3 H), 2.95–3.28 (m , 3 H), 2.68–2.86 (m ,
2 H), 2.22–2.50 (m , 3 H), 1.85–1.97 (m , 1 H), 1.47–1.74 (m , 2 H). MS (EI), m/z (%): 301 (5),
88 (11), 86 (65), 84 (100), 83 (12), 49 (18), 47 (23). HRMS (EI): for C17H19NO4 calculated
301.1314, foun d 301.1316.
14-Hydroxydihydrocodeine (20). Th e title com poun d was isolated followin g th e protocol for
biotran sform ation s usin g Trametes sanguinea (ATCC 14622) in 10–15% yield as colorless oil.
Data (1H NMR an d 13C NMR) for com poun d 20 were foun d to be iden tical to th e m ajor
isom er obtain ed from th e reduction of oxycodon e with sodium boroh ydride in m eth an ol.
20
RF 0.35 (DCM/MeOH/NH4OH, 98:2:1); [α]D –93.1 (c 0.65, CHCl3) (lit.25 [α]D –169 (c 0.6,
CHCl3); –138 (c 1.8, 10% HOAc)). 1H NMR (CDCl3, 600 MHz): 6.78 (d, J = 8.2, 1 H), 6.62 (d,
J = 8.2, 1 H), 4.78 (d, J = 6.5, 1 H), 4.12–4.29 (m , 1 H), 3.88 (s, 3 H), 3.14 (d, J = 18.5, 1 H),
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1179–1193