Hydrochloric Acid → Diphenylmethyl (4R, 6R, 7R)-3(1-hydroxybut 3enyl)7phenylacetamidoceph-2em-4carboxylate

HRID 2417151Notes

Reaction equation

HRID 2417151 reaction equation
[CH2:1]([Mg]Cl)[CH:2]=[CH2:3].[CH:6]([C:8]1[C@H:13]([C:14]([O:16][CH:17]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[O:15])[N:12]2[C:30](=[O:42])[C@@H:31]([NH:32][C:33](=[O:41])[CH2:34][C:35]3[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=3)[C@H:11]2[S:10][CH:9]=1)=[O:7].[Cl-].[Li+].Cl>O1CCCC1.C(OCC)(=O)C>[OH:7][CH:6]([C:8]1[C@H:13]([C:14]([O:16][CH:17]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[O:15])[N:12]2[C:30](=[O:42])[C@@H:31]([NH:32][C:33](=[O:41])[CH2:34][C:35]3[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=3)[C@H:11]2[S:10][CH:9]=1)[CH2:3][CH:2]=[CH2:1]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 433294Lithium ChlorideHCID 113527753-Formyl-7betaphenylacetylamino-ceph-2-em-4alpha-carboxylic acid diphenylmethyl esterHCID 178418473HCID 178418473, compound

Product 1

HCID 131724666Diphenylmethyl (4R, 6R, 7R)-3(1-hydroxybut 3enyl)7phenylacetamidoceph-2em-4carboxylate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Allylmagnesium chloride (2M in diethyl ether, 4.0 ml, 8 mmol) was added to a solution containing diphenylmethyl (4R, 6R, 7R)-3-formyl-7-phenylacetamidoceph-2-em-4-carboxylate (0.5 g, 1.0 mmol) and lithium chloride (0.35 g, 8 mmol) in tetrahydrofuran (5 ml) at −70° C. After 20 minutes at −70° C., hydrochloric acid (1M, 10 ml, 10 mmol) was added. Ethyl acetate was added and the organic layer was separated, washed with brine, dried (MgSO4), and evaporated. The resulting oil was purified by chromatography (20% to 60% ethyl acetate in hexane, silica gel) giving; first the title compound S-diastereomer, 90 mg (17%), dH (CDCl3) 2.18 (1H, dt, J 15 Hz and 8 Hz), 2.36 (1H, dt, J 17 and 5 Hz), 3.45 (2H, ABq), 4.18 (1H, m), 4.95-5.15 (4H, m), 5.55-5.7 (2H, m), 6.11 (1H, d, J 9 Hz), 6.36 (1H, s), 6.89 (1H, s), 7.3-7.4 (15H, m), and second; the title compound R-diastereomer, 250 mg (45%), dH (CDCl3) 2.28 (2H, t, J 7 Hz), 3.62 (2H, ABq), 4.15 (1H, t, J 7 Hz), 4.95-5.2 (4H, m), 5.5-5.65 (2H, m), 6.16 (1H, d, J 9 Hz), 6.20 (1H, s), 6.89 (1H, s), 7.3-7.4 (15H, m).

Workup

  1. customthe organic layer was separated
  2. washwashed with brine
  3. dry with materialdried (MgSO4)
  4. customevaporated
  5. customThe resulting oil was purified by chromatography (20% to 60% ethyl acetate in hexane, silica gel)
  6. customgiving

Sources & evidence

ORD record
ord-b0984b8bfa2b4762bec7e4afc18f1312
Source dataset
uspto-grants-2004_11
Patent number
US06825344B2

Reaction notes

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