m-Chloroperbenzoic acid → (8R,9S,13S,14S,17R)-4-Fluoro-17-hydroxy-13-methyl-17-[(1-oxidopyridin-1-ium-4-yl)methyl]-7,8,9,11,12,14,15,16-octahydro-6H-cyclopenta[a]phenanthrene-3-carbonitrile

HRID 926110Notes

Reaction equation

[CH3:1][C@@:2]12[C@:10]([OH:18])([CH2:11][C:12]3[CH:17]=[CH:16][N:15]=[CH:14][CH:13]=3)[CH2:9][CH2:8][C@H:7]1[C@@H:6]1[CH2:19][CH2:20][C:21]3[C:26]([F:27])=[C:25]([C:28]#[N:29])[CH:24]=[CH:23][C:22]=3[C@H:5]1[CH2:4][CH2:3]2.ClC1C=C(C=CC=1)C(OO)=[O:35]>ClCCl>[CH3:1][C@@:2]12[C@:10]([OH:18])([CH2:11][C:12]3[CH:13]=[CH:14][N+:15]([O-:35])=[CH:16][CH:17]=3)[CH2:9][CH2:8][C@H:7]1[C@@H:6]1[CH2:19][CH2:20][C:21]3[C:26]([F:27])=[C:25]([C:28]#[N:29])[CH:24]=[CH:23][C:22]=3[C@H:5]1[CH2:4][CH2:3]2

Participants

Conditions

Temperature: 22 °C

Procedure

To a solution of EM-5855 (86 mg, 0.22 mmol) in anhydrous dichloromethane (5 mL) at 0° C. was added 3-chloroperoxybenzoic acid (54 mg, 0.22 mmol). The mixture was stirred for 16 h at 22° C. and evaporated to dryness. The crude compound was purified by flash chromatography (silica gel, 0-10% methanol in chloroform) to give 67 mg (75%) of EM-5854. 1H NMR (400 MHz, CDCl3) δ: 0.94 (s, 3H, Me), 2.57 (d, Jgem=13.5 Hz, 1H, —CH2-Pyr), 2.68 (m, 1H, H-6), 2.93 (d, Jgem=13.3 Hz, 2H, —CH2-Pyr, H-6), 7.17 (d, J=8.3 Hz, 1H, Ar), 7.27 (d, J=6.0 Hz, 2H, Pyr), 7.36 (t, J=7.7 Hz., 1H, Ar), 8.01 (d, J=6.8 Hz, 2H, Pyr).

Workup

customevaporated to dryness
customThe crude compound was purified by flash chromatography (silica gel, 0-10% methanol in chloroform)

Sources & evidence

ORD record: ord-2cb81b313d1b40ff9bd3f012c69e389d
Source dataset: uspto-grants-2016_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09284345B2

Reaction notes

Loading…