Benzophenone imine → HCID 86640814, compound

HRID 2070881Notes

Reaction equation

HRID 2070881 reaction equation
[CH3:1][C:2]1[C:10]2[C:5](=[N:6][CH:7]=[C:8]([NH2:11])[CH:9]=2)[N:4]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[N:3]=1.BrC1C=C2C(C)=NN(COCC[Si](C)(C)C)C2=NC=1.[C:39]1([C:45]([C:47]2[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=2)=N)[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1.C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1>[C:39]1([C:45]([C:47]2[CH:48]=[CH:49][CH:50]=[CH:51][CH:52]=2)=[N:11][C:8]2[CH:9]=[C:10]3[C:2]([CH3:1])=[N:3][N:4]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:18])([CH3:17])[CH3:19])[C:5]3=[N:6][CH:7]=2)[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1

Participants

7

Reactant 5

HCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 592764783-Methyl-1-[[2-(trimethylsilyl)ethoxy]methyl]-1H-pyrazolo[3,4-b]pyridin-5-amineHCID 685867915-Bromo-3-methyl-1-[[2-(trimethylsilyl)ethoxy]methyl]-1H-pyrazolo[3,4-b]pyridine

Product 1

HCID 86640814HCID 86640814, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
115 °C

Procedure

3-Methyl-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-b]pyridin-5-amine. A degassed mixture of 5-bromo-3-methyl-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-b]pyridine (1.7 g, 5 mmol), diphenylmethanimine (1.36 g, 7.5 mmol), tris(dibenzylideneacetone)palladium (0) (920 mg, 1 mmol), (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (1.55 g, 2.5 mmol), and sodium tert-butoxide (720 mg, 7.5 mmol) in toluene (30 mL) was heated at 115° C. under nitrogen overnight. The reaction mixture was concentrated, and purified by column chromatography on silica gel (eluting with 5-20% ethyl acetate in petroleum ether) to give N-(diphenylmethylene)-3-methyl-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-b]pyridin-5-amine (2.5 g, crude), which was dissolved in tetrahydrofuran (10 mL), and hydrochloric acid (2 N, 10 mL) was added. The mixture was stirred at room temperature for 2 h. The mixture was adjusted to pH=8 with saturated sodium carbonate solution, extracted with ethyl acetate, dried, concentrated, and purified by column chromatography on silica gel (eluting with 10-25% ethyl acetate in petroleum ether) to give 3-methyl-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-b]pyridin-5-amine (1.1 g, 79.1% yield) as an oil. 1H NMR (400 MHz, CHLOROFORM-d) δ (ppm) 8.10 (s, 1H), 7.18 (s, 1H), 5.7 (s, 1H), 3.58 (d, J=11.2 Hz, 2H), 3.34 (s, 2H), 2.47 (s, 3H), 0.90 (t, J=11.2 Hz, 2H), −0.09 (s, 9H).

Workup

  1. concentrationThe reaction mixture was concentrated
  2. custompurified by column chromatography on silica gel (eluting with 5-20% ethyl acetate in petroleum ether)

Sources & evidence

ORD record
ord-03fa80d420e144c5ae6781f0112e2850
Source dataset
uspto-grants-2012_10
Patent number
US08299056B2

Reaction notes

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