Tetrabutylammonium Fluoride → HCID 10316055, compound

HRID 507255Notes

Reaction equation

HRID 507255 reaction equation
CCCC[N+](CCCC)(CCCC)CCCC.[F-].C([Si](C1C=CC=CC=1)(C1C=CC=CC=1)[O:24][CH2:25][CH2:26][CH2:27][N:28]1[C:32]2=[N:33][CH:34]=[CH:35][CH:36]=[C:31]2[C:30]([C:37]2[C:38](=[O:49])[NH:39][C:40](=[O:48])[C:41]=2[C:42]2[O:43][CH2:44][CH2:45][CH2:46][CH:47]=2)=[CH:29]1)(C)(C)C>C1COCC1>[O:43]1[C:42]([C:41]2[C:40](=[O:48])[NH:39][C:38](=[O:49])[C:37]=2[C:30]2[C:31]3[C:32](=[N:33][CH:34]=[CH:35][CH:36]=3)[N:28]([CH2:27][CH2:26][CH2:25][OH:24])[CH:29]=2)=[CH:47][CH2:46][CH2:45][CH2:44]1

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 21912003HCID 21912003, compound

Product 1

HCID 10316055HCID 10316055, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Tributyl-(5,6-dihydro-4H-pyran-2-yl)-stannane Compound 15e (0.051 mL, 0.13 mmol) was added to a solution of 3-{1-[3-(tert-butyl-diphenyl-silanyloxy)-propyl]-1H-pyrrolo[2,3-b]pyridin-3-yl}-4-chloro-pyrrole-2,5-dione Compound 15d (0.054 g, 0.1 mmol), PdCl2(PPh3)2 (0.007 g, 0.01 mmol) and lithium chloride (0.013 g, 0.3 mmol) in DMF (1.5 mL) at 23° C. under nitrogen. The reaction mixture was heated to 100° C. and stirred for 18 h. After cooling to 23° C., the mixture was diluted with EtOAc (10 mL), washed with H2O (3×10 mL), sat'd KF (1×10 mL) and brine (1×10 mL), then dried (MgSO4) and concentrated. The product was purified by column chromatography (SiO2) to give Compound 15f (0.027 g, 46%) as a yellow solid. 1H NMR (300 MHz, CDCl3) δ 8.34 (dd, J=4.7, 1.5 Hz, 1H), 7.96 (dd, J=8.7, 2.3 Hz, 1H), 7.93 (s, 1H), 7.66 (m, 4H), 7.38 (m, 6H), 7.13 (dd, J=7.9, 4.7 Hz, 1H), 5.78 (t, J=4.3 Hz, 2H), 4.52 (t, J=7.0 Hz, 2H), 3.83 (m, 2H), 3.74 (t, J=5.8 Hz, 2H), 2.29 (m, 2H), 2.16 (m, 2H), 1.86 (m, 2H), 1.08 (s, 9H); MS (ES) m/z: 592 (M+H+). TBAF (0.07 mL, 0.07 mmol; 1 M solution in THF) was added dropwise to a solution of 3-{1-[3-(tert-butyl-diphenyl-silanyloxy)-propyl]-1H-pyrrolo[2,3-b]pyridin-3-yl}-4-(5,6-dihydro-4H-pyran-2-yl)-pyrrole-2,5-dione Compound 15f (0.027 g, 0.046 mmol) in THF (2 mL) under nitrogen. After 18 hours the mixture was concentrated and purified by column chromatography (SiO2) to give Compound 23 (0.011 g, 70%) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ 8.34 (d, J=4.6 Hz, 1H), 7.99 (d, J=8.1 Hz, 1H), 7.90 (s, 1H), 7.51 (br s, 1H), 7.18 (dd, J=7.9, 4.6 Hz, 1H), 5.87 (t, J=4.2 Hz, 1H), 4.66 (m, 1H), 4.51 (t, J=6.0 Hz, 2H), 3.82 (t, J=4.9 Hz, 2H), 3.43 (m, 2H), 2.31 (m, 2H), 2.04 (m, 2H), 1.85 (m, 2H); MS (ES) m/z: 354 (M+H+).

Workup

  1. concentrationAfter 18 hours the mixture was concentrated
  2. custompurified by column chromatography (SiO2)

Sources & evidence

ORD record
ord-973af293952b40608f982a03b590b329
Source dataset
uspto-grants-2010_08
Patent number
US07786135B2

Reaction notes

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