Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)- → ((3aR,4R,6R,6aS)-6-(6-chloro-9H-purin-9-yl)-2-ethoxytetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)methanol

HRID 511562Notes

Reaction equation

HRID 511562 reaction equation
[NH2:1][C:2]1[C:3]([NH:9][C@@H:10]2[CH2:14][C@H:13]([CH2:15][OH:16])[C@@H:12]([OH:17])[C@H:11]2[OH:18])=[N:4][CH:5]=[N:6][C:7]=1[Cl:8].[CH:19]([O-])([O-])[O:20][CH2:21][CH3:22].[C:25]12(CS(O)(=O)=O)C(C)(C)C(CC1)CC2=O>>[Cl:8][C:7]1[N:6]=[CH:5][N:4]=[C:3]2[C:2]=1[N:1]=[CH:25][N:9]2[C@H:10]1[C@@H:11]2[O:18][CH:19]([O:20][CH2:21][CH3:22])[O:17][C@@H:12]2[C@@H:13]([CH2:15][OH:16])[CH2:14]1

Participants

4

Reactant 3

HCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 10978690(1R,2S,3R,5R)-3-((5-amino-6-chloropyrimidin-4-yl)amino)-5-(hydroxymethyl)cyclopentane-1,2-diolHCID 53630039Ethylorthoformate

Product 1

HCID 86666106((3aR,4R,6R,6aS)-6-(6-chloro-9H-purin-9-yl)-2-ethoxytetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)methanol

Procedure

The above crude (1R,2S,3R,5R)-3-((5-amino-6-chloropyrimidin-4-yl)amino)-5-(hydroxymethyl)cyclopentane-1,2-diol was treated with ethyl orthoformate (120 mL, 720 mmol) and 10-camphorsulfonic acid (8.11 g, 34.9 mmol). The heterogeneous brown mixture was stirred vigorously to afford a nearly homogeneous brown solution after 10 min. At 5 h, LC MS indicated the desired product as the major product and the reaction was quenched with saturated aqueous NaHCO3 (120 mL). The mixture was diluted with water (75 mL), extracted with CH2Cl2 (3×200 mL), and the combined organics were dried (Na2SO4) and concentrated in vacuo to afford the crude title compound as a dark brown liquid, which was carried on without further manipulation: MS (ESI+) for C14H17ClN4O4 m/z 341.0 (M+H)+.

Workup

  1. customto afford a nearly homogeneous brown solution after 10 min

Sources & evidence

ORD record
ord-202fffd44e974878be7f7485ebc3b9e3
Source dataset
uspto-grants-2015_08
Patent number
US09096634B2

Reaction notes

Loading…