3-((R)-7-bromo-4-methyl-3-oxo-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino)-3-methyl-azetidine-1-carboxylic acid tert-butyl ester → (R)-7-bromo-4-methyl-6-(3-methyl-azetidin-3-ylamino)-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one

HRID 519149Notes

Reaction equation

HRID 519149 reaction equation
C(OC([N:8]1[CH2:11][C:10]([NH:13][C:14]2[CH:15]=[C:16]3[C:25](=[CH:26][C:27]=2[Br:28])[O:24][CH2:23][C:22]2[N:17]3[C@H:18]([CH3:30])[C:19](=[O:29])[NH:20][N:21]=2)([CH3:12])[CH2:9]1)=O)(C)(C)C>C(O)(C(F)(F)F)=O.C(Cl)Cl>[Br:28][C:27]1[CH:26]=[C:25]2[C:16]([N:17]3[C:22]([CH2:23][O:24]2)=[N:21][NH:20][C:19](=[O:29])[C@H:18]3[CH3:30])=[CH:15][C:14]=1[NH:13][C:10]1([CH3:12])[CH2:9][NH:8][CH2:11]1

Participants

4

Reactant 1

HCID 867275233-((R)-7-bromo-4-methyl-3-oxo-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino)-3-methyl-azetidine-1-carboxylic acid tert-butyl ester

Product 1

HCID 86727542(R)-7-bromo-4-methyl-6-(3-methyl-azetidin-3-ylamino)-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-oneYield 101.2%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 6422Trifluoroacetic acidSolvent

Procedure

A solution of 3-((R)-7-bromo-4-methyl-3-oxo-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino)-3-methyl-azetidine-1-carboxylic acid tert-butyl ester (Example #148, Step G, 5 g, 10.4 mmol) in TFA (4 mL) and DCM (24 mL) was stirred at ambient temperature for 3 h. The solvent was removed in vacuo to give (R)-7-bromo-4-methyl-6-(3-methyl-azetidin-3-ylamino)-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one (4 g, 100%). 1H NMR (400 MHz, DMSO-d6) δ 10.77 (s, 1H), 7.19 (s, 1H), 5.83 (s, 1H), 5.55 (s, 1H), 4.91 (q, J=6.4 Hz, 1H), 4.51 (s, 2H), 4.05 (m, 4H), 1.55 (s, 3H), 1.25 (d, J=6.4 Hz, 3H). LC/MS (Table 1, Method 6) Rt=0.656 min.; MS m/z: 380 [M+H]+ and 382 [M+H+2]+.

Workup

  1. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-fa6cb097ad9e4dfda3be9db65547342c
Source dataset
uspto-grants-2015_08
Patent number
US09115151B2

Reaction notes

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