tert-Butanol → HCID 25234712, compound

HRID 508375Notes

Reaction equation

HRID 508375 reaction equation
[C:1]([C:5]1[C:6]([O:35][CH3:36])=[C:7]([CH:24]=[C:25]([N:27]2[CH:32]=[CH:31][C:30](=[O:33])[NH:29][C:28]2=[O:34])[CH:26]=1)/[CH:8]=[CH:9]/[C:10]1[CH:18]=[CH:17][C:16]([NH:19][S:20]([CH3:23])(=[O:22])=[O:21])=[CH:15][C:11]=1C(O)=O)([CH3:4])([CH3:3])[CH3:2].C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:44])C=CC=CC=1.C([N:56]([CH2:59]C)CC)C.[C:61]([OH:65])([CH3:64])([CH3:63])[CH3:62]>>[C:1]([C:5]1[C:6]([O:35][CH3:36])=[C:7]([CH:24]=[C:25]([N:27]2[CH:32]=[CH:31][C:30](=[O:33])[NH:29][C:28]2=[O:34])[CH:26]=1)/[CH:8]=[CH:9]/[C:10]1[CH:18]=[CH:17][C:16]([NH:19][S:20]([CH3:23])(=[O:22])=[O:21])=[CH:15][C:11]=1[NH:56][C:59](=[O:44])[O:65][C:61]([CH3:64])([CH3:63])[CH3:62])([CH3:3])([CH3:4])[CH3:2]

Participants

5

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 25234654HCID 25234654, compound

Product 1

HCID 25234712HCID 25234712, compoundYield 19%

Conditions

Temperature
80 °C

Procedure

To a solution of the product from Example 125 (75 mg, 0.146 mmol) in tert-butanol (4 ml) was added diphenylphosphoryl azide (47 μL 0.219 mmol) and triethylamine (31 μL, 0.219 mmol). The resulting mixture was stirred at 80° C. for 18 h. The cooled mixture was partitioned between H2O (10 ml) and EtOAc (2×10 ml). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The crude product was purified by column chromatography on silica gel using 3% MeOH in CH2Cl2 as the eluent to give the title compound (16 mg, 19%). 1H NMR (300 MHz, DMSO-d6) δ 11.45 (d, J=1.84 Hz, 1H) 9.86 (s, 1H) 9.03 (s, 1H) 7.75 (d, J=7.72 Hz, 2H) 7.55 (d, J=2.57 Hz, 1H) 7.10-7.33 (m, 4H) 7.04 (dd, J=8.64, 2.39 Hz, 1H) 5.66 (dd, J=7.91, 2.02 Hz, 1H) 3.78 (s, 3H) 3.02 (s, 3H) 1.45 (s, 9H) 1.38 (s, 9H).

Workup

  1. customThe cooled mixture was partitioned between H2O (10 ml) and EtOAc (2×10 ml)
  2. dry with materialThe combined organic layers were dried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customThe crude product was purified by column chromatography on silica gel using 3% MeOH in CH2Cl2 as the eluent

Sources & evidence

ORD record
ord-bad2cc8d86b846e6a9945e168f09b9df
Source dataset
uspto-grants-2015_08
Patent number
US09095590B2

Reaction notes

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