Tetrabutylammonium Fluoride → HCID 67984007, compound

HRID 1397170Notes

Reaction equation

HRID 1397170 reaction equation
[Si](OCC(OCC1C=CC=CC=1)=O)(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.C([SiH2][O:35][C:36](C1C=CC=CC=1)(C1C=CC=CC=1)[C:37]1[C:42]([C:43]2[CH:48]=[CH:47][N:46]=[C:45]([NH:49][C:50]3[CH:55]=[CH:54][N:53]=[CH:52][CH:51]=3)[N:44]=2)=[CH:41][N:40]=[C:39]([NH2:56])[N:38]=1)(C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>>[NH2:56][C:39]1[N:38]=[C:37]([CH2:36][OH:35])[C:42]([C:43]2[CH:48]=[CH:47][N:46]=[C:45]([NH:49][C:50]3[CH:51]=[CH:52][N:53]=[CH:54][CH:55]=3)[N:44]=2)=[CH:41][N:40]=1

Participants

4

Reactant 3

HCID 2724141Tetrabutylammonium Fluoride2×HCID 21162312HCID 21162312, compoundHCID 131731280HCID 131731280, compound

Product 1

HCID 67984007HCID 67984007, compound

Procedure

This compound was synthesized in an analogous manner to 21 utilizing benzyl 2-(tert-butyldiphenylsilyloxy)acetate in step one, and further TBDPS deprotection as the last step. To 4′-(tert-Butyl-diphenyl-silanyloxymethyl)-N2-pyridin-4-yl-[4,5]bipyrimidinyl-2,2′-diamine (150 mg, 0.281 mmol), TBAF (1N in THF) (562 μl, 0.562 mmol) was added. The reaction was stirred rt for 1 hour. Additional TBAF (1N in THF) (281 μl, 0.281 mmol) was added, and the reaction mixture was stirred for an additional 2 hours. The reaction was quenched by slow addition of saturated ammonium chloride and the volatiles were evaporated. The residue was then partitioned between water and EtOAc. The organic layer was washed with brine, dried with sodium sulfate, and concentrated. The crude product was purified by reverse-phase HPLC [100% aqueous phase to 60% organic phase over 15 minutes] to obtain the desired product as a slightly pale yellow solid (50 mg, 60% yield). 1H NMR (400 MHz, DMSO-d6) ppm 4.66 (d, J=2.53 Hz, 2 H) 5.04 (br. s., 1 H) 7.18 (s, 2 H) 7.30 (d, J=5.05 Hz, 1 H) 7.77 (d, J=6.06 Hz, 2 H) 8.36 (d, J=6.06 Hz, 2 H) 8.57 (d, J=5.56 Hz, 1 H) 8.63 (s, 1 H) 10.03 (s, 1 H). HRMS (ES+) for C14H13N7O.H+ [MH+]: calcd. 296.1260. found 296.1263. UV-LC: 100/100% UV purity at 214/254 nm; tR=2.87 minutes over 7.75 minutes

Workup

  1. stirringthe reaction mixture was stirred for an additional 2 hours
  2. customThe reaction was quenched by slow addition of saturated ammonium chloride
  3. customthe volatiles were evaporated
  4. customThe residue was then partitioned between water and EtOAc
  5. washThe organic layer was washed with brine
  6. dry with materialdried with sodium sulfate
  7. concentrationconcentrated
  8. customThe crude product was purified by reverse-phase HPLC [100% aqueous phase to 60% organic phase over 15 minutes]

Sources & evidence

ORD record
ord-801fab3095ba480780aa82b0ed90eb26
Source dataset
uspto-grants-2014_12
Patent number
US08901147B2

Reaction notes

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