Pyridine → HCID 131731073, compound

HRID 1910657Notes

Reaction equation

HRID 1910657 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:21]([OH:22])[C@:20]([CH3:24])([OH:23])[C@@H:19]([CH2:25][O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28])[O:18][C@H:10]1[O:11][CH2:12][CH2:13][Si:14]([CH3:17])([CH3:16])[CH3:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CC=CC=1.Cl[C:41]([O:43][C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1)=[O:42]>C(Cl)Cl>[CH2:1]([O:8][C@@H:9]1[C@@H:21]([O:22][C:41]([O:43][C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)=[O:42])[C@:20]([CH3:24])([OH:23])[C@@H:19]([CH2:25][O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28])[O:18][C@H:10]1[O:11][CH2:12][CH2:13][Si:14]([CH3:16])([CH3:15])[CH3:17])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 1049PyridineHCID 15891Phenyl chloroformateHCID 68733124HCID 68733124, compound

Product 1

HCID 131731073HCID 131731073, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Compound 5.09 (4.0 g, 8.0 mmol) was dissolved in CH2Cl2 (80 mL) and pyridine (2.6 mL, 32 mmol) then chilled to 0° C. Phenyl chloroformate (1.1 mL, 8.8 mmol) was added and the reaction was stirred for 20 min then quenched with 20 mL MeOH and concentrated in vacuo. The residue was dissolved in CH2Cl2 then washed with H2O and brine. The organic layer was concentrated in vacuo and the residue was purified by silica gel chromatography (10% EtOAc/petroleum ether) to afford the title compound (5.0 g, 8.0 mmol, 100%). 1H NMR (500 MHz, CDCl3): δ ppm 7.36-7.25 (m, 7H, PhH), 7.22 (t, J=7.3 Hz, 1H, PhH), 7.10 (d, J=8.8 Hz, 2H, PhH), 4.97 (d, J=10.3 Hz, 1H, H-3), 4.95, 4.67 (ABq, J=11.2 Hz, OCH2Ph1H each,), 4.53 (d, J=7.8 Hz, 1H, H-1), 4.04-3.96 (m, 1H, OCHHCH2SiMe3), 3.89 (d, J=7.3 Hz, 2H, H-6), 3.64 (s, 1H, OH), 3.63-3.58 (m, 1H, OCHHCH2SiMe3), 3.54 (t, J=7.1 Hz, 1H, H-5), 3.38 (dd, J=10.3, 7.8 Hz, 1H, H-2), 1.36 (s, 3H, Me), 1.04 (t, J=8.8 Hz, 2H, OCH2CH2SiMe3), 0.91 (s, 9H, SiCMe3), 0.13, 0.12 (s, 3H each, SiMe2), 0.04 (s, 9H, SiMe3); 13C NMR (125 MHz, CDCl3): δ ppm 153.72, 151.34, 138.51, 129.43, 128.44, 127.66, 127.64, 125.97, 121.18, 103.63, 83.26, 79.14, 75.22, 74.80, 73.57, 68.06, 62.56, 25.94, 18.69, 18.26, 16.13, −1.29, −5.38, −5.55; HRMS calcd for C32H54NO8Si2 [M+NH4]+: 618.3044. found 618.9056.

Workup

  1. customthen quenched with 20 mL MeOH
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in CH2Cl2
  4. washthen washed with H2O and brine
  5. concentrationThe organic layer was concentrated in vacuo
  6. customthe residue was purified by silica gel chromatography (10% EtOAc/petroleum ether)

Sources & evidence

ORD record
ord-6236f31b3211446c90320879cc3fce5a
Source dataset
uspto-grants-2013_12
Patent number
US08604004B2

Reaction notes

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