Lithium Chloride → (2S,4S)-2-hydroxymethyl-N-(p-nitrobenzyloxycarbonyl)-4-tritylthiopyrrolidine

HRID 259999Notes

Reaction equation

HRID 259999 reaction equation
[C:1]1([C:7]([C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[S:8][C@@H:9]2[CH2:13][N:12]([C:14]([O:16][CH2:17][C:18]3[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][CH:19]=3)=[O:15])[C@H:11]([C:27](OC)=[O:28])[CH2:10]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[BH4-].[Na+].[Cl-].[Li+]>O1CCCC1.C(O)C.C(OCC)(=O)C.Cl>[C:37]1([C:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)([C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)[S:8][C@@H:9]2[CH2:13][N:12]([C:14]([O:16][CH2:17][C:18]3[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][CH:19]=3)=[O:15])[C@H:11]([CH2:27][OH:28])[CH2:10]2)[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=1

Participants

8

Reactant 3

HCID 433294Lithium ChlorideHCID 4311764Sodium borohydrideHCID 57167581(2S,4S)-4-triphenylmethylthio-2-methoxycarbonyl-1-p-nitrobenzyloxycarbonylpyrrolidine

Product 1

HCID 15056118(2S,4S)-2-hydroxymethyl-N-(p-nitrobenzyloxycarbonyl)-4-tritylthiopyrrolidineYield 88%

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of (2S,4S)-4-triphenylmethylthio-2-methoxycarbonyl-1-p-nitrobenzyloxycarbonylpyrrolidine (3: 3.63 g) in tetrahydrofuran (36 ml) under ice cooling are added a solution of sodium borohydride (371 mg) in ethanol (15 ml) and a solution of lithium chloride (554 mg) in tetra-hydrofuran (15 ml), and the mixture is warmed to room temperature and stirred for 110 minutes. The reaction mixture is diluted with ethyl acetate under ice cooling, neutralized with 1N-hydrochloric acid (10 ml) to decompose remaining reagent. The organic layer is taken, washed with water and saturated brine, dried over sodium sulfate, and concentrated in vacuo. The residue is purified by silica gel chromatography to give (2S,4S)-4-triphenylmethylthio-2-hydroxymethyl-1-p-nitrobenzyloxycarbonylpyrrolidine (4: 3.02 g) as colorless foam. Yield: 88%. IR ν (CHCl3) cm-1 : 3400, 1679, 1603. 1HNMR δ (CDCl3) ppm: 1.3 to 2.13(2H, m), 1.6(1H, brs), 2.65 to 4.3(6H, m), 5.03 to 5.2(2H, m), 7.07 to 7.55(17H, m), 8.15 to 8.3(2H, m).

Workup

  1. washwashed with water and saturated brine
  2. dry with materialdried over sodium sulfate
  3. concentrationconcentrated in vacuo
  4. customThe residue is purified by silica gel chromatography

Sources & evidence

ORD record
ord-3776ac51f3de4bcda09132f99b474589
Source dataset
uspto-grants-1996_06
Patent number
US05523415

Reaction notes

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