Sodium borohydride → Ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(hydroxy)acetate

HRID 2406398Notes

Reaction equation

HRID 2406398 reaction equation
Cl.[CH2:2]([O:5][C:6]1[CH:11]=[C:10]([CH3:12])[CH:9]=[CH:8][C:7]=1[C:13]1[C:18]([C:19](=[O:25])[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[C:17]([CH3:26])[N:16]=[C:15]2[S:27][C:28]3[CH2:33][CH2:32][CH2:31][CH2:30][C:29]=3[C:14]=12)[CH:3]=[CH2:4].[BH4-].[Na+]>C(O)C>[CH2:2]([O:5][C:6]1[CH:11]=[C:10]([CH3:12])[CH:9]=[CH:8][C:7]=1[C:13]1[C:18]([CH:19]([OH:25])[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[C:17]([CH3:26])[N:16]=[C:15]2[S:27][C:28]3[CH2:33][CH2:32][CH2:31][CH2:30][C:29]=3[C:14]=12)[CH:3]=[CH2:4]

Participants

4

Reactant 2

HCID 4311764Sodium borohydrideHCID 69672800Ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(oxo)acetate hydrochloride salt

Product 1

HCID 69672380Ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(hydroxy)acetateYield 91%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a stirred solution of ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(oxo)acetate hydrochloride salt (Step 6, 1.1 g, 2.56 mmol) in ethanol (20 mL) was added sodium borohydride (145 mg, 3.84 mmol), and the reaction was stirred at room temperature for 5 minutes. The reaction was concentrated in vacuo, and the residue was partitioned between ethyl acetate (20 mL) and hydrochloric acid (aqueous, 1 N, 30 mL). The organic layer was separated, washed with brine (10 mL), dried over MgSO4, filtered and concentrated in vacuo to give a mixture of diastereoisomers of the title compound as a pale orange gum, 1.1 g, in a 91% yield. LCMS (2 min acidic) 1.53 min 52-81% pure by UV, ES+/AP+ 452. 1HNMR (400 MHz, CDCl3 δ ppm 1.17-1.21 (m, 3H), 1.53-1.64 (m, 2H), 1.71-1.87 (m, 4H), 2.43 (s, 3H), 2.63 (s, 3H), 2.81 (t, 2H), 4.08-4.22 (m, 2H), 4.47-4.51 (m, 2H), 5.08-5.17 (m, 2H), 5.18 (s, 1H), 5.86 (m, 1H), 6.79 (s, 1H), 6.81-6.85 (m, 1H), 7.02 (d, 1H).

Workup

  1. concentrationThe reaction was concentrated in vacuo
  2. customthe residue was partitioned between ethyl acetate (20 mL) and hydrochloric acid (aqueous, 1 N, 30 mL)
  3. customThe organic layer was separated
  4. washwashed with brine (10 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give

Sources & evidence

ORD record
ord-d9b95f6d560442cba7f6b00c5ed3e9e0
Source dataset
uspto-grants-2014_08
Patent number
US08809363B2

Reaction notes

Loading…