Pyridine → HCID 86669982, compound

HRID 1475132Notes

Reaction equation

HRID 1475132 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@@H:6]1[CH2:24][CH2:25][P:26](=[O:33])([O:30][CH2:31][CH3:32])[O:27]CC)(=[O:3])[CH3:2].[N:34]1[CH:39]=[CH:38]C=[CH:36][CH:35]=1.[Si](Br)(C)(C)C>CC#N>[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@@H:6]1[CH2:24][CH2:25][P:26](=[O:27])([O-:30])[O-:33])(=[O:3])[CH3:2].[CH2:35]([NH+:34]([CH2:31][CH3:32])[CH2:39][CH3:38])[CH3:36].[CH2:35]([NH+:34]([CH2:31][CH3:32])[CH2:39][CH3:38])[CH3:36]

Participants

5

Reactant 3

HCID 1049PyridineHCID 76113BromotrimethylsilaneHCID 11317948HCID 11317948, compound

Product 1

HCID 86669982HCID 86669982, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 5a (260 mg, 0.53 mmol) in CH3CN (5 mL) at 0° C., pyridine (450 μL, 5.52 mmol, 10.5 equiv.) was added, followed by Me3SiBr (730 μL, 5.52 mmol, 10.5 equiv.). The solution was stirred at 0° C. for 3 h. The reaction was quenched with H2O/C5H5N (9:1, 5 mL) and the solution was evaporated to dryness. The residue was purified by Purification Method 1 (0-50% MeOH against 0.05 M TEAB) to afford the triethylammonium salt of phosphonic acid 6 in quantitative yield (230 mg, 0.52 mmol): Rf 0.1 (EtOAc/EtOH 20:1); δH (400 MHz, CDCl3) 5.25 (dd, 1H, J5,6 and J6,7 2.4 Hz, H-6), 5.15-5.05 (m, 2H, H-4, H-5), 4.14-3.95 (m, 4H, H-3, H-7, H-8a, H-8b), 2.98 (q, 6H, J 7.3 Hz, NCH2CH3), 1.85-1.30 (m, 4H, H-1a, H-1b, H-2a, H-2b), 1.06 (t, 7.6H, J 7.3 Hz, NCH2CH3); δC (100 MHz, CDCl3) 72.3 (d, JC,P 14.3 Hz, C-3), 68.4, 68.3, 68.2 (C-4/C-5/C-6/C-7), 62.0 (C-8), 46.7 (NCH2CH3), 22.5 (d, JC,P 136.4 Hz, C-1), 20.2, 20.0 (4×C(O)CH3), 19.3 (C-2), 8.3 (NCH2CH3). m/z (ESI) 439.0999 [M−H]−, C16H24O12P requires 439.1011.

Workup

  1. customThe reaction was quenched with H2O/C5H5N (9:1, 5 mL)
  2. customthe solution was evaporated to dryness
  3. customThe residue was purified by Purification Method 1 (0-50% MeOH against 0.05 M TEAB)

Sources & evidence

ORD record
ord-1c6af7be475b44dfa6adb73f7bf308de
Source dataset
uspto-grants-2015_04
Patent number
US09018370B2

Reaction notes

Loading…