Toluene → HCID 66599117, compound

HRID 2191210Notes

Reaction equation

HRID 2191210 reaction equation
[CH3:1][C:2]1[CH:29]=[C:28]([CH3:30])[C:5]2[N:6]([C:18]([O:20][CH2:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[O:19])[CH2:7][CH2:8][CH2:9]/[C:10](=[N:11]/[C:12]3[N:13]=[N:14][N:15]([CH3:17])[N:16]=3)/[C:4]=2[CH:3]=1.CC1C=C(C)C2N(C(OCC3C=CC=CC=3)=O)CCC=C(NC3N=NN(C)N=3)C=2C=1.C1(C)C=CC=CC=1>>[CH3:1][C:2]1[CH:29]=[C:28]([CH3:30])[C:5]2[N:6]([C:18]([O:20][CH2:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[O:19])[CH2:7][CH2:8][CH2:9][C@H:10]([NH:11][C:12]3[N:13]=[N:14][N:15]([CH3:17])[N:16]=3)[C:4]=2[CH:3]=1

Participants

4

Reactant 3

HCID 1140TolueneHCID 66599326HCID 66599326, compoundHCID 87067435HCID 87067435, compound

Product 1

HCID 66599117HCID 66599117, compound

Conditions

Temperature
100 °C

Procedure

Charge an autoclave with a mixture of (Z)-benzyl 7,9-dimethyl-5-(2-methyl-2H-tetrazol-5-ylimino)-2,3,4,5-tetrahydro-1H-benzo[b]azepine-1-carboxylate and (E)-benzyl 7,9-dimethyl-5-(2-methyl-2H-tetrazol-5-ylamino)-2,3-dihydro-1H-benzo[b]azepine-1-carboxylate (4.04 g, 10 mmole), S-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl ((S)-BINAP, 60 mg, 96.3 μmoles), KI (415 mg 24 mmoles, KI can be deleted if desired) and di chloro-bis((1,2,5,6 eta)-1,5-cyclooctadiene)diiridium (Ir2Cl2(COD)2 (927 mg 40.2 μmoles). Purge the autoclave with nitrogen. While maintaining an oxygen free environment, add degassed toluene (50 mL, 472.8 mmol) and seal the autoclave. Heat to 100° C. under 500 psi H2 for 66 h. Cool the reaction mixture to RT and vent. Filter the solids and collect the organic mixture. Wash the organic mixture with water (2×25 mL); dry over Na2SO4, and filter. Collect the filtrate and remove the solvent under vacuum to provide the title compound (3.99 g, 88.7% ee by HPLC).

Workup

  1. additionCharge an autoclave
  2. customPurge the autoclave with nitrogen
  3. temperatureWhile maintaining an oxygen free environment
  4. additionadd
  5. customseal the autoclave
  6. temperatureCool the reaction mixture to RT
  7. filtrationFilter the solids
  8. customcollect the organic mixture
  9. washWash the organic mixture with water (2×25 mL)
  10. dry with materialdry over Na2SO4
  11. filtrationfilter
  12. customCollect the filtrate
  13. customremove the solvent under vacuum

Sources & evidence

ORD record
ord-762216c48ab046a185e282fc02900400
Source dataset
uspto-grants-2012_12
Patent number
US08329688B2

Reaction notes

Loading…