tert-butyl ((11bR)-3,3,11b-trimethyl-10-nitro-4,4-dioxido-4a,5,6,11b-tetrahydro-3H-benzo[6,7]oxepino[4,5-b][1,4]thiazin-2-yl)carbamate → tert-butyl ((11bR)-10-amino-3,3,11b-trimethyl-4,4-dioxido-4a,5,6,11b-tetrahydro-3H-benzo[6,7]oxepino[4,5-b][1,4]thiazin-2-yl)carbamate

HRID 627604Notes

Reaction equation

HRID 627604 reaction equation
[CH3:1][C:2]1([CH3:31])[S:7](=[O:9])(=[O:8])[CH:6]2[CH2:10][CH2:11][O:12][C:13]3[CH:18]=[CH:17][C:16]([N+:19]([O-])=O)=[CH:15][C:14]=3[C@@:5]2([CH3:22])[N:4]=[C:3]1[NH:23][C:24](=[O:30])[O:25][C:26]([CH3:29])([CH3:28])[CH3:27]>CCOC(C)=O.CCO.[Pd]>[NH2:19][C:16]1[CH:17]=[CH:18][C:13]2[O:12][CH2:11][CH2:10][CH:6]3[S:7](=[O:8])(=[O:9])[C:2]([CH3:31])([CH3:1])[C:3]([NH:23][C:24](=[O:30])[O:25][C:26]([CH3:27])([CH3:28])[CH3:29])=[N:4][C@:5]3([CH3:22])[C:14]=2[CH:15]=1

Participants

5

Reactant 1

HCID 90307368tert-butyl ((11bR)-3,3,11b-trimethyl-10-nitro-4,4-dioxido-4a,5,6,11b-tetrahydro-3H-benzo[6,7]oxepino[4,5-b][1,4]thiazin-2-yl)carbamate

Product 1

HCID 90307363tert-butyl ((11bR)-10-amino-3,3,11b-trimethyl-4,4-dioxido-4a,5,6,11b-tetrahydro-3H-benzo[6,7]oxepino[4,5-b][1,4]thiazin-2-yl)carbamate

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalyst2×HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of tert-butyl ((11bR)-3,3,11b-trimethyl-10-nitro-4,4-dioxido-4a,5,6,11b-tetrahydro-3H-benzo[6,7]oxepino[4,5-b][1,4]thiazin-2-yl)carbamate (190 mg, 0.419 mmol) (1.9:1 mixture of trans/cis epimers) in EtOAc (3 ml) and EtOH (1.000 ml) was hydrogenated (balloon) in the presence of palladium (10% wt. on activated carbon) (44.6 mg, 0.042 mmol) for 2 hr at rt. Additional palladium, 10% wt. on activated carbon (44.6 mg, 0.042 mmol) was added and hydrogenation continued for additional 2 h. The mixture was filtered through the plug of celite and washed 3 times with 3 ml portions of EtOAc. The filtrate was concentrated in vacuo to give tert-butyl ((11bR)-10-amino-3,3,11b-trimethyl-4,4-dioxido-4a,5,6,11b-tetrahydro-3H-benzo[6,7]oxepino[4,5-b][1,4]thiazin-2-yl)carbamate as a mixture of diastereomers which was used in the next step without purification.

Workup

  1. customfor 2 hr
  2. customat rt
  3. filtrationThe mixture was filtered through the plug of celite
  4. washwashed 3 times with 3 ml portions of EtOAc
  5. concentrationThe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-d078037b05884df19623dda2317af53c
Source dataset
uspto-grants-2016_04
Patent number
US09309263B2

Reaction notes

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