3-Cyanophenylboronic acid → HCID 67176039, compound

HRID 2096609Notes

Reaction equation

Br[C:2]1[CH:24]=[CH:23][C:5]2[O:6][CH2:7][CH:8]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[CH2:9][C:10]3([O:14][N:13]([CH3:15])[C:12]([NH2:16])=[N:11]3)[C:4]=2[CH:3]=1.[C:25]([C:27]1[CH:28]=[C:29](B(O)O)[CH:30]=[CH:31][CH:32]=1)#[N:26]>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>[NH2:16][C:12]1[N:13]([CH3:15])[O:14][C:10]2([CH2:9][CH:8]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)[CH2:7][O:6][C:5]3[CH:23]=[CH:24][C:2]([C:31]4[CH:32]=[C:27]([CH:28]=[CH:29][CH:30]=4)[C:25]#[N:26])=[CH:3][C:4]2=3)[N:11]=1

Participants

Conditions

Temperature: 120 °C

Procedure

Pd(PPh3)2Cl2 (3 mg, 0.003 mmol) in a 10 mL of flask under Ar2 was treated sequentially with 7-bromo-2′-methyl-3-phenyl-3,4-dihydro-2H,2′H-spiro[benzo[b]oxepine-5,5′-[1,2,4]oxadiazol]-3′-amine (77.4 mg, 0.2 mmol) in [1,4]dioxane (2.0 mL), Cs2CO3 (2 N, 1 mL) and 3-cyanophenylboronic acid (58.8 mg, 0.4 mmol) The mixture was heated under 120° C. at Ar2 under microwave for 30 minutes. The reaction mixture was concentrated in vacuo to give the residue, which was purified preparative TLC and HPLC to give 3-(3′-amino-2′-methyl-3-phenyl-3,4-dihydro-2H,2′H-spiro[benzo[b]oxepine-5,5′-[1,2,4]oxadiazole]-7-yl)benzonitrile (20 mg, 24%). 1H-NMR (MeOD): 2.67 (m, 2H), 3.48 (m, 3H), 3.65 (m, 1H), 3.88 (m, 0.3H), 4.19 (m, 0.7H), 4.50 (d, 1H), 7.23 (m, 6H), 7.66 (m, 3H), 7.81 (m, 1H), 8.02 (m, 3H).

Workup

concentrationThe reaction mixture was concentrated in vacuo
customto give the residue, which
customwas purified preparative TLC and HPLC

Sources & evidence

ORD record: ord-0471f7945f094fde8c252d33a48d81b0
Source dataset: uspto-grants-2013_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08450308B2

Reaction notes

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