Lithium hydroxide, monohydrate → HCID 69624759, compound

HRID 397290Notes

Reaction equation

HRID 397290 reaction equation
C([O:3][C:4](=[O:66])[CH:5]([NH:55][C:56]([O:58][CH2:59][C:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1)=[O:57])[CH2:6][C:7]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[NH:9][C:8]=1[C@H:16]1[O:45][C@H:44]([CH2:46][O:47][CH2:48][C:49]2[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=2)[C@@H:35]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@H:26]([O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C@@H:17]1[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)C.O.[OH-].[Li+]>COCCOC.O>[C:56]([NH:55][C@H:5]([CH2:6][C:7]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[NH:9][C:8]=1[C@H:16]1[O:45][C@H:44]([CH2:46][O:47][CH2:48][C:49]2[CH:50]=[CH:51][CH:52]=[CH:53][CH:54]=2)[C@@H:35]([O:36][CH2:37][C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[C@H:26]([O:27][CH2:28][C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[C@@H:17]1[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:4]([OH:66])=[O:3])([O:58][CH2:59][C:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1)=[O:57].[C:56]([NH:55][C@@H:5]([CH2:6][C:7]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[NH:9][C:8]=1[C@H:16]1[O:45][C@H:44]([CH2:46][O:47][CH2:48][C:49]2[CH:50]=[CH:51][CH:52]=[CH:53][CH:54]=2)[C@@H:35]([O:36][CH2:37][C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[C@H:26]([O:27][CH2:28][C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[C@@H:17]1[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:4]([OH:66])=[O:3])([O:58][CH2:59][C:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1)=[O:57]

Participants

6

Reactant 2

HCID 168937Lithium hydroxide, monohydrateHCID 69624731HCID 69624731, compound2×

Product 2

HCID 69624759HCID 69624759, compoundYield 40%HCID 69624790HCID 69624790, compoundYield 17%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

First, 1.72 g (1.94 mmol) of 2-[N-(carbobenzyloxy)amino]-3-[2-(2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl)indole-3-yl]propionic acid ethyl ester [compound (XI) wherein R1 to R4 are benzyl, R6 is ethyl and Ar is phenyl) was dissolved in 1,2-dimethoxyethane (60 ml)-water (30 ml). Then, 0.24 g (5.82 mmol) of lithium hydroxide monohydrate was added to the mixture and stirred at room temperature for about 16 hours. After the reaction was terminated, 0.5N citric acid (30 ml) was added to the reacted mixture which was then subjected to extraction with dichloromethane. The extracted solution was washed with water and then dried on anhydrous sodium sulfate. After removal of solvent, the residue was fractionated by columun chromatography on silica gel [silica gel: Merck Rieselgel 60 (230-400 mesh ASTM); elution solvent: n-hexane, ethyl acetate and methanol (3:6:0.6)] to elute compound (XII-1) and then compound (XII-2) which were further purified by preparative thin layer chromatography [preparative thin layer plate: Merck Kieselgel 60 F254 (1 mm thick); development solvent: n-hexane, ethyl acetate and methanol (3:6:0.5)] to give 0.66 g (yield 40%) of (2R*)-2-[N-(carbobenzyloxy)amino]-3-[2-(2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl)indole-3-yl]propionic acid [compound (XII-1) wherein R1 to R4 are benzyl and Ar is phenyl] and 0.29 g (yield 17%) of (2S*)-2-[N-(carbobenzyloxy) amino]-3-(2-(2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl)indole-3-yl]propionic acid [compound (XII-2) wherein R1 to R4 are benzyl and Ar is phenyl].

Workup

  1. customAfter the reaction was terminated
  2. addition0.5N citric acid (30 ml) was added to the reacted mixture which
  3. extractionwas then subjected to extraction with dichloromethane
  4. washThe extracted solution was washed with water
  5. dry with materialdried on anhydrous sodium sulfate
  6. customAfter removal of solvent
  7. washto elute compound (XII-1)
  8. customcompound (XII-2) which were further purified by preparative thin layer chromatography [preparative thin layer plate: Merck Kieselgel 60 F254 (1 mm thick); development solvent: n-hexane, ethyl acetate and methanol (3:6:0.5)]

Sources & evidence

ORD record
ord-09caa2a736b04b069ed83073c7c479cb
Source dataset
uspto-grants-2003_08
Patent number
US06610502B1

Reaction notes

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