3-Cyanophenylboronic acid → HCID 58423857, compound

HRID 1408596Notes

Reaction equation

HRID 1408596 reaction equation
[NH2:1][C:2]1[N:3]([CH3:25])[C:4](=[O:24])[C:5]2([C:15]3[C:10](=[CH:11][CH:12]=[C:13](Br)[CH:14]=3)[O:9][CH:8]([C:17]3[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=3)[CH2:7]2)[N:6]=1.[C:26]([C:28]1[CH:29]=[C:30](B(O)O)[CH:31]=[CH:32][CH:33]=1)#[N:27]>O1CCOCC1.C([O-])([O-])=O.[Cs+].[Cs+].Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:1][C:2]1[N:3]([CH3:25])[C:4](=[O:24])[C@:5]2([C:15]3[C:10](=[CH:11][CH:12]=[C:13]([C:32]4[CH:33]=[C:28]([CH:29]=[CH:30][CH:31]=4)[C:26]#[N:27])[CH:14]=3)[O:9][C@H:8]([C:17]3[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=3)[CH2:7]2)[N:6]=1.[NH2:1][C:2]1[N:3]([CH3:25])[C:4](=[O:24])[C:5]2([C:15]3[C:10](=[CH:11][CH:12]=[C:13]([C:32]4[CH:33]=[C:28]([CH:29]=[CH:30][CH:31]=4)[C:26]#[N:27])[CH:14]=3)[O:9][CH:8]([C:17]3[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=3)[CH2:7]2)[N:6]=1

Participants

7

Reactant 2

HCID 27343253-Cyanophenylboronic acidHCID 58424018HCID 58424018, compound

Product 2

HCID 58423857HCID 58423857, compoundYield 10%HCID 58424224HCID 58424224, compoundYield 8%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 10796Cesium carbonateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

Pd(PPh3)2Cl2 (10 mg) in a 10 mL of tube under Ar2 was treated sequentially with 2′-amino-6-bromo-2-(4-fluorophenyl)-1′-methylspiro[chroman-4,4′-imidazol]-5′(1′H)-one (40 mg, 0.099 mmol) in 1,4-dioxane (1 mL), Cs2CO3 (2 N, 0.3 mL) and 3-cyanophenylboronic acid (29 mg, 0.197 mmol). The mixture was heated under microwave at 120° C. for 30 min. The reaction mixture was concentrated in vacuo to give the residue, which was purified by preparative TLC and then by preparative HPLC to give pure 3-((2S,4S)-2′-amino-2-(4-fluorophenyl)-1′-methyl-5′-oxo-1′,5′-dihydrospiro[chroman-4,4′-imidazole]-6-yl)benzonitrile (19a) (6 mg, 10%), 1H-NMR (MeOD): 2.41 (t, 1H), 2.60 (t, 1H), 3.10 (s, 3H), 5.83 (d, 1H), 7.16 (m, 3H), 7.52 (m, 2H), 7.60 (m, 2H), 7.69 (m, 2H), 7.90 (m, 1H), 7.99 (d, 1H), and 3-(2′-amino-2-(4-fluorophenyl)-1′-methyl-5′-oxo-1′,5′-dihydrospiro[chrom-an-4,4′-imidazole]-6-yl)benzonitrile (19) (4 mg, 8%), 1H-NMR (MeOD): 2.42 (t, 1H), 2.60 (t, 1H), 3.20 (s, 3H), 5.87 (d, 1H), 7.19 (m, 3H), 7.45 (m, 2H), 7.51 (m, 1H), 7.54 (m, 1H), 7.64 (m, 2H), 7.90 (t, 1H), 7.99 (d, 1H).

Workup

  1. concentrationThe reaction mixture was concentrated in vacuo
  2. customto give the residue, which
  3. customwas purified by preparative TLC

Sources & evidence

ORD record
ord-e30ce964e459416d994b62e062e8d442
Source dataset
uspto-grants-2014_12
Patent number
US08921359B2

Reaction notes

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