Sodium cyanoborohydride → ethyl 1-[2-(N-benzyloxycarbonyl-N-methylamino)ethyl]4-piperidinylideneacetate

HRID 354518Notes

Reaction equation

HRID 354518 reaction equation
[CH2:1]([O:8][C:9]([N:11]([CH2:13][CH:14]=O)[CH3:12])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH:16]1[CH2:21][CH2:20][C:19](=[CH:22][C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:18][CH2:17]1.[BH3-]C#N.[Na+]>CO.CC(O)=O>[CH2:1]([O:8][C:9]([N:11]([CH2:13][CH2:14][N:16]1[CH2:21][CH2:20][C:19](=[CH:22][C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:18][CH2:17]1)[CH3:12])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 5003444Sodium cyanoborohydrideHCID 12010768Benzyl N-methyl-N-(2-oxoethyl)carbamateHCID 18695502Ethyl 2-(piperidin-4-ylidene)acetate

Product 1

HCID 23512137ethyl 1-[2-(N-benzyloxycarbonyl-N-methylamino)ethyl]4-piperidinylideneacetateYield 47.4%

Reagents, catalysts & solvents 1

HCID 10129899Acetic acid methanolSolvent

Procedure

To a stirred solution of 2-(N-benzyloxycarbonyl-N-methylamino)acetaldehyde (2.07 g, 10.0 mmol) and ethyl 4-piperidinylideneacetate (1.69 g, 10.0 mmol) in MeOH—AcOH (10:1, v/v, 22 ml) was added NaBH3CN (1.32 g, 20 mmol) and the stirring was continued overnight. The mixture was quenched by addition of sat. NaHCO3 (200 ml) and extracted with CHCl3 (3×150 ml). The combined extracts were dried over MgSO4 and evaporated. The residue was chromatographed on silica-gel with CHCl3—EtOH (40:1, v/v) to give ethyl 1-[2-(N-benzyloxycarbonyl-N-methylamino)ethyl]4-piperidinylideneacetate (1.71 g, 47%) as a colorless oil. 1H-NMR (CDCl3) δ1.25 (t, J=7.3 Hz, 3 H), 2.16 (m, 2 H), 2.57 (m, 4 H), 2.95 (m, 7 H), 3.44 (m, 2 H), 4.13 (q, J=7.3 Hz, 2 H), 5.12 (s, 2 H), 5.49-5.53 (m, 1 H), 7.35 (m, 5 H).

Workup

  1. customThe mixture was quenched by addition of sat. NaHCO3 (200 ml)
  2. extractionextracted with CHCl3 (3×150 ml)
  3. dry with materialThe combined extracts were dried over MgSO4
  4. customevaporated
  5. customThe residue was chromatographed on silica-gel with CHCl3—EtOH (40:1, v/v)

Sources & evidence

ORD record
ord-7fee8bc635fc4035abf1420171d68469
Source dataset
uspto-grants-2004_06
Patent number
US06756378B2

Reaction notes

Loading…