Sodium Carbonate → 5-(7-methyl-2H,3H-benzo[e]1,4-dioxin-6-yl)-2-pyridylamine

HRID 874666Notes

Reaction equation

HRID 874666 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5](B2OC(C)(C)C(C)(C)O2)=[CH:4][N:3]=1.Br[C:18]1[C:19]([CH3:28])=[CH:20][C:21]2[O:26][CH2:25][CH2:24][O:23][C:22]=2[CH:27]=1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.CC#N.CC(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)C.CC(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)C.Cl[Pd]Cl>[CH3:28][C:19]1[C:18]([C:5]2[CH:6]=[CH:7][C:2]([NH2:1])=[N:3][CH:4]=2)=[CH:27][C:22]2[O:23][CH2:24][CH2:25][O:26][C:21]=2[CH:20]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27565555-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-amineHCID 124645496-Bromo-7-methyl-2,3-dihydro-1,4-benzodioxine

Product 1

HCID 584873735-(7-methyl-2H,3H-benzo[e]1,4-dioxin-6-yl)-2-pyridylamineYield 26%

Reagents, catalysts & solvents 3

HCID 11714597Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II)CatalystHCID 6342AcetonitrileSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
85 °C

Procedure

The 2-aminopyridine-5-boronic acid pinacol ester (400 mg, 1.8 mmol) and 182 (550 mg, 2 mmol) was dissolved in 2 mL 1,4-dioxane and 2 mL MeCN. The 4 ml of 2 M Na2CO3 was added and the mixture was bubbled with Ar for 2 min before bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) (A-Phos, 70 mg, 0.1 mmol) was added. The reaction was heated at 85° C. for 2 h. The reaction mixture was worked-up with EtOAc extraction. The product was purified by flash column and afforded 183 (112.4 mg, 26%) as yellow oil. LC-MS: calcd. for C14H14N2O2: 243 (M+1).

Workup

  1. additionwas added
  2. extractionThe reaction mixture was worked-up with EtOAc extraction
  3. customThe product was purified by flash column

Sources & evidence

ORD record
ord-4991d9ac135b4947b7d28eafb069a11d
Source dataset
uspto-grants-2015_03
Patent number
US08980629B2

Reaction notes

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