Lithium borohydride → HCID 86755667, compound

HRID 1872456Notes

Reaction equation

HRID 1872456 reaction equation
[CH2:1]([O:3][C:4]([C@@H:6]1[C@@H:11]2[C@H:7]1[CH2:8][C:9](=[O:26])[C@@:10]2([NH:22][C:23](=[O:25])[CH3:24])[C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13])=[O:5])[CH3:2].[Li+].[BH4-]>CCO.C1COCC1>[CH2:1]([O:3][C:4]([C@@H:6]1[C@@H:11]2[C@H:7]1[CH2:8][C@@H:9]([OH:26])[C@@:10]2([NH:22][C:23](=[O:25])[CH3:24])[C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13])=[O:5])[CH3:2].[CH2:1]([O:3][C:4]([C@@H:6]1[C@@H:11]2[C@H:7]1[CH2:8][C@H:9]([OH:26])[C@@:10]2([NH:22][C:23](=[O:25])[CH3:24])[C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13])=[O:5])[CH3:2]

Participants

6

Reactant 2

HCID 4148881Lithium borohydrideHCID 86755666HCID 86755666, compound

Product 2

HCID 86755667HCID 86755667, compoundHCID 86755668HCID 86755668, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-50 °C

Procedure

To a solution of (1S,2R,5R,6S)-2-acetylamino-3-oxo-bicyclo [3.1.0] hexane-2,6-dicarboxylic 2-benzyl ester 6-ethyl ester (XVI) (77 mg, 0.214 mmol) in EtOH (2 mL) and THF (1 mL) was added LiBH4 (5 mg, 0.23 mmol) at -50° C. and the mixture was stirred at -50° C. for 45 min. The reaction was quenched by addition of 1 N HCl (ca. 0.5 mL), warming up to 23° C. and stirring for 10 min. After dilution with ethyl acetate and extraction with sat. NaHCO3 -sol., brine and drying over MgSO4 the crude product was purified by silica gel column chromatography with toluene/acetone 3:1 to give (1S,2R,3R,5R,6S)-2-acetylamino-3-hydroxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid 2-benzyl ester 6-ethyl ester (XVII) (33 mg, 43%, less polar product) as a colorless oil and (1S,2R,3S,5R,6S)-2-acetylamino-3-hydroxy-bicyclo[3.1.0]hexane-2,6-dicarboxylic acid 2-benzyl ester 6-ethyl ester (XVIII) (35 mg, 45%, more polar product) as a white solid. (XVII): 1H-NMR (250 MHz, CDCl3) □1.26 (3H, t, J=7.2 Hz), 1.76 (1H, t, J=3.5 Hz), 2.07 (1H, m), 2.10 (3H, s), 2.16 (1H, dd, J=6.1, 3.0 Hz), 2.30-2.41 (3H, m), 3.97-4.13 (3H, m), 5.24 (2H, bs), 6.19 (1H, bs), 7.26-7.38 (5H, m); MS[ISP] 362 (M+H+); □D20 -11.24° (c=1.18, CHCl3). (XVIII): 1H-NMR (250 MHz, CDCl3) □1.25 (3H, t, J=7.1 Hz), 1.98 (1H, m), 2.05-2.11 (1H, m),2.06 (3H, s), 2.18 (1H,t,J=3.5 Hz), 2.27-2.41 (2H, m), 2.59 (1H, ddd,J=13, 7, 5 Hz), 4.12 (2H, m), 4.68 (1H, dd, J=7, 5 Hz), 5.17 (2H, s), 6.30 (1H, bs), 7.26-7.40 (5H, m); MS[ISP] 362 (M+H+); mp 145-147° C.; □D20 +42.44° (c=1.01, CHCl3).

Workup

  1. customThe reaction was quenched by addition of 1 N HCl (ca. 0.5 mL)
  2. temperaturewarming up to 23° C.
  3. stirringstirring for 10 min
  4. extractionAfter dilution with ethyl acetate and extraction with sat. NaHCO3 -sol
  5. dry with material, brine and drying over MgSO4 the crude product
  6. customwas purified by silica gel column chromatography with toluene/acetone 3:1

Sources & evidence

ORD record
ord-15393f82e8cd401c93e39cc7b276dbcd
Source dataset
uspto-grants-2000_08
Patent number
US06107342

Reaction notes

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