p-Toluenesulfonic acid → (rac.)-(1R*,5S*)-7-(4-Hydroxy-phenyl)-3,9-diaza-bicyclo[3.3.1]non-6-ene-3,6,9-tricarboxylic Acid 3-tert-butyl Ester 6-ethyl Ester 9-(2,2,2-trichloro-1,1-dimethyl-ethyl) Ester

HRID 2428174Notes

Reaction equation

HRID 2428174 reaction equation
[Cl:1][C:2]([Cl:45])([Cl:44])[C:3]([O:6][C:7]([N:9]1[C@H:14]2[C:15]([C:32]([O:34][CH2:35][CH3:36])=[O:33])=[C:16]([C:18]3[CH:23]=[CH:22][C:21]([O:24][Si](C(C)(C)C)(C)C)=[CH:20][CH:19]=3)[CH2:17][C@@H:10]1[CH2:11][N:12]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:13]2)=[O:8])([CH3:5])[CH3:4].CC1C=CC(S(O)(=O)=O)=CC=1.C([O-])([O-])=O.[Na+].[Na+]>CO>[Cl:45][C:2]([Cl:1])([Cl:44])[C:3]([O:6][C:7]([N:9]1[C@H:14]2[C:15]([C:32]([O:34][CH2:35][CH3:36])=[O:33])=[C:16]([C:18]3[CH:23]=[CH:22][C:21]([OH:24])=[CH:20][CH:19]=3)[CH2:17][C@@H:10]1[CH2:11][N:12]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:13]2)=[O:8])([CH3:4])[CH3:5]

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 10340Sodium CarbonateHCID 131728969(rac.)-(1R*,5S*)-7-[4-(tert-Butyl-dimethyl-silanyloxy)-phenyl]-3,9-diaza-bicyclo[3.3.1]non-6-ene-3,6,9-tricarboxylic Acid 3-tert-butyl Ester 6-ethyl Ester 9-(2,2,2-trichloro-1,1-dimethyl-ethyl) Ester

Product 1

HCID 131728970(rac.)-(1R*,5S*)-7-(4-Hydroxy-phenyl)-3,9-diaza-bicyclo[3.3.1]non-6-ene-3,6,9-tricarboxylic Acid 3-tert-butyl Ester 6-ethyl Ester 9-(2,2,2-trichloro-1,1-dimethyl-ethyl) EsterYield 33.2%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Compound B10 (7.58 g, 10.7 mmol) was dissolved in MeOH (110 mL) and p-TsOH (2.03 g, 11.8 mmol) was added. The mixture was stirred at rt for 2 h, and aq. 10% Na2CO3 (200 mL) was added. The solvents were partially removed under reduced pressure, and the resulting suspension was extracted with EtOAc. The org. extracts were filtered and washed with aq. 10% Na2CO3 and brine. The org. layer was dried over Na2SO4, filtered, and the solvents were removed under reduced pressure. Purification of the crude by FC (EtOAc/heptane) yielded the title compound (2.10 g, 33%). LC-MS: tR=1.09 min, ES+: 593.25.

Workup

  1. customThe solvents were partially removed under reduced pressure
  2. extractionthe resulting suspension was extracted with EtOAc
  3. filtrationextracts were filtered
  4. washwashed with aq. 10% Na2CO3 and brine
  5. dry with materiallayer was dried over Na2SO4
  6. filtrationfiltered
  7. customthe solvents were removed under reduced pressure
  8. customPurification of the crude by FC (EtOAc/heptane)

Sources & evidence

ORD record
ord-82174afaffa546f58b83ae33c8ffca63
Source dataset
uspto-grants-2011_06
Patent number
US07968720B2

Reaction notes

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