Ethyl Acetate → 4-(5-Chloro-2-methylbenzoxazol-6-yl)phenylamine

HRID 407105

Reaction equation

Br[C:2]1[C:11]([Cl:12])=[CH:10][C:5]2[N:6]=[C:7]([CH3:9])[O:8][C:4]=2[CH:3]=1.Cl.[NH2:14][C:15]1[CH:20]=[C:19](B(O)O)[CH:18]=[CH:17][CH:16]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].CC(=O)OCC>C(#N)C.O1CCOCC1.O.CCCCCC.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>[Cl:12][C:11]1[C:2]([C:18]2[CH:19]=[CH:20][C:15]([NH2:14])=[CH:16][CH:17]=2)=[CH:3][C:4]2[O:8][C:7]([CH3:9])=[N:6][C:5]=2[CH:10]=1

Participants

Conditions

Temperature: 85 °C

Procedure

A mixture of 6-bromo-5-chloro-2-methylbenzoxazole (54) (160 mg, 0.65 mmol), anilin-5-boronic acid hydrochloride salt (55) (135 mg, 1.2 eq), Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium (II) (A-Phos) (46 mg, 0.1 mmol) and K3PO4 (165 mg) in 2 ml ACN, 2 ml dioxane and 0.5 ml H2O was bubbled with argon before heated at 85° C. for 2 h. After cooling down to r.t., the reaction mixture was taken up in EA, washed with aq. NaHCO3 and brine, dried over Na2SO4, concentrated to dryness. The resulting red solid was dissolved in DCM and subjected to silica gel column purification using 0-60% B (A: hexane; B: 50% EA in hexane) to furnish 70.6 mg 56 as yellow solid (yield: 42%)

Workup

customwas bubbled with argon
temperatureAfter cooling down to r.t.
washwashed with aq. NaHCO3 and brine
dry with materialdried over Na2SO4
concentrationconcentrated to dryness
dissolutionThe resulting red solid was dissolved in DCM
customsubjected to silica gel column purification

Sources & evidence

ORD record: ord-f85e768951b248fc8c2ae6801d6e5f25
Source dataset: uspto-grants-2014_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08754219B2

Linked notes

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