Water → (1S,2R,3S,4R,5S)-4-(2-Chloro-6-((1-(4-fluoro-3-nitrophenyl)-1H-1,2,3-triazol-4-yl)methylamino)-9H-purin-9-yl)-2,3-dihydroxy-N-methylbicyclo[3.1.0]hexane-1-carboxamide

HRID 1896231Notes

Reaction equation

HRID 1896231 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]=[N+:9]=[N-:10])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].[Cl:14][C:15]1[N:23]=[C:22]2[C:18]([N:19]=[CH:20][N:21]2[C@@H:24]2[C@@H:29]3[C@@:27]([C:30]([NH:32][CH3:33])=[O:31])([CH2:28]3)[C@@H:26]([OH:34])[C@H:25]2[OH:35])=[C:17]([NH:36][CH2:37][C:38]#[CH:39])[N:16]=1.O.O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+]>C(O)(C)(C)C.S([O-])([O-])(=O)=O.[Cu+2].CCCC[Sn](OC(C)=O)(CCCC)CCCC>[Cl:14][C:15]1[N:23]=[C:22]2[C:18]([N:19]=[CH:20][N:21]2[C@@H:24]2[C@@H:29]3[C@@:27]([C:30]([NH:32][CH3:33])=[O:31])([CH2:28]3)[C@@H:26]([OH:34])[C@H:25]2[OH:35])=[C:17]([NH:36][CH2:37][C:38]2[N:10]=[N:9][N:8]([C:5]3[CH:6]=[CH:7][C:2]([F:1])=[C:3]([N+:11]([O-:13])=[O:12])[CH:4]=3)[CH:39]=2)[N:16]=1

Participants

8

Reactant 4

HCID 962WaterHCID 931211-Fluoro-2-nitro-4-azidobenzeneHCID 23667548Sodium AscorbateHCID 86672501HCID 86672501, compound

Product 1

HCID 86672500(1S,2R,3S,4R,5S)-4-(2-Chloro-6-((1-(4-fluoro-3-nitrophenyl)-1H-1,2,3-triazol-4-yl)methylamino)-9H-purin-9-yl)-2,3-dihydroxy-N-methylbicyclo[3.1.0]hexane-1-carboxamideYield 92%

Reagents, catalysts & solvents 3

HCID 24462Copper SulfateCatalystHCID 16682741Tributyltin acetateCatalystHCID 6386tert-ButanolSolvent

Procedure

4-Fluoro-3-nitro-phenylazide (9.7 mg, 0.053 mmol) and TBTA (1 mg, 0.001 mmol) were added to a solution of compound 218 (14.4 mg, 0.038 mmol) in t-butanol (0.8 mL)-water (0.8 mL) at room temperature. Freshly prepared 1M solution of sodium ascorbate (38.2 μL) followed by 7.5% solution of copper sulfate (63 μL, 0.019 mmol) was also added into the reaction mixture stirred at room temperature overnight. Solvent was evaporated, and the residue was purified on flash silica gel column chromatography (CH2Cl2:MeOH=30:1) to give compound 219a (19 mg, 92%) as a syrup. 1H NMR (CD3OD, 400 MHz) δ 8.62-8.61 (m, 2H), 8.27-8.24 (m, 1H), 8.06 (s, 1H), 7.69-7.64 (m, 1H), 5.08 (d, J=6.8 Hz, 1H), 4.94 (br s, 2H), 4.81 (s, 1H), 4.01 (d, J=6.0 Hz, 1H), 2.87 (s, 3H), 2.07-2.04 (m, 1H), 1.82 (t, J=4.8 Hz, 1H), 1.39-1.37 (m, 1H). HRMS calculated for C22H21ClFN10O5 (M+H)+: 559.1369. Found 559.1346.

Workup

  1. additionwas also added into the reaction mixture
  2. customSolvent was evaporated
  3. customthe residue was purified on flash silica gel column chromatography (CH2Cl2:MeOH=30:1)

Sources & evidence

ORD record
ord-568fab321a654552875384824a02f29e
Source dataset
uspto-grants-2013_08
Patent number
US08518957B2

Reaction notes

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