Cesium carbonate → 5'-(3-chloro-5-fluorophenyl)-5,6,8,9-tetrahydro-3'H-spiro[benzo[7]annulene-7,2'-benzofuran]-3'-one

HRID 1503416Notes

Reaction equation

HRID 1503416 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[O:9][C:8]3([CH2:15][CH2:14][C:13]4[CH:16]=[CH:17][CH:18]=[CH:19][C:12]=4[CH2:11][CH2:10]3)[C:7](=[O:20])[C:6]=2[CH:21]=1.[Cl:22][C:23]1[CH:24]=[C:25](B(O)O)[CH:26]=[C:27]([F:29])[CH:28]=1.C([O-])([O-])=O.[Cs+].[Cs+].O1CCOCC1>C(Cl)Cl.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.O>[Cl:22][C:23]1[CH:24]=[C:25]([C:2]2[CH:3]=[CH:4][C:5]3[O:9][C:8]4([CH2:10][CH2:11][C:12]5[CH:19]=[CH:18][CH:17]=[CH:16][C:13]=5[CH2:14][CH2:15]4)[C:7](=[O:20])[C:6]=3[CH:21]=2)[CH:26]=[C:27]([F:29])[CH:28]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 15391287(3-Chloro-5-fluorophenyl)boronic acidHCID 581970305'-bromo-5,6,8,9-tetrahydro-3'H-spiro[benzo[7]annulene-7,2'-benzofuran]-3'-one

Product 1

HCID 581980625'-(3-chloro-5-fluorophenyl)-5,6,8,9-tetrahydro-3'H-spiro[benzo[7]annulene-7,2'-benzofuran]-3'-oneYield 92.5%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
110 °C

Procedure

A 10 mL microwave tube was charged with 5′-bromo-5,6,8,9-tetrahydro-3′H-spiro[benzo[7]annulene-7,2′-benzofuran]-3′-one (0.0573 g, 0.167 mmol), 3-chloro-5-fluorophenylboronic acid (0.0930 g, 0.53 mmol), Cs2CO3 (0.2537 g, 0.78 mmol), 1,4-dioxane (4 mL), water (1 mL), and PdCl2(PPh3)2 (0.0118 g, 0.0168 mmol). The tube was heated in a CEM microwave reactor at 110° C. for 30 min. The reaction mixture was diluted with CH2Cl2 and dried over Na2SO4. After the solvent was evaporated under reduced pressure, the residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford 0.0607 g (92%) of 5′-(3-chloro-5-fluorophenyl)-5,6,8,9-tetrahydro-3′H-spiro[benzo[7]annulene-7,2′-benzofuran]-3′-one. LC-MS tR=2.55 min in 3 min chromatography, m/z 393, 395 (MH+).

Workup

  1. dry with materialdried over Na2SO4
  2. customAfter the solvent was evaporated under reduced pressure
  3. customthe residue was purified by chromatography on silica gel
  4. washeluted with hexanes/ethyl acetate

Sources & evidence

ORD record
ord-93571cb8376847198f3efa9d5c4453b8
Source dataset
uspto-grants-2015_12
Patent number
US09212153B2

Reaction notes

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