(R)-2-[2-bromo-4-fluoro-6-(prop-1-enyl)phenoxy]but-3-enyl 4-methylbenzenesulfonate → (R)-(8-bromo-6-fluoro-2H-chromen-2-yl)methyl-4-methylbenzenesulfonate

HRID 902316Notes

Reaction equation

HRID 902316 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([O:11][CH2:12][C@H:13]([O:16][C:17]2[C:22]([CH:23]=CC)=[CH:21][C:20]([F:26])=[CH:19][C:18]=2[Br:27])[CH:14]=C)(=[O:10])=[O:9])=[CH:4][CH:3]=1>ClCCl.C(P(C1CCCCC1)(C1CCCCC1)C1CCCCC1)(P(C1CCCCC1)(C1CCCCC1)C1CCCCC1)C1C=CC=CC=1.Cl[Ru]Cl>[Br:27][C:18]1[CH:19]=[C:20]([F:26])[CH:21]=[C:22]2[C:17]=1[O:16][C@@H:13]([CH2:12][O:11][S:8]([C:5]1[CH:6]=[CH:7][C:2]([CH3:1])=[CH:3][CH:4]=1)(=[O:10])=[O:9])[CH:14]=[CH:23]2

Participants

4

Reactant 1

HCID 86609112(R)-2-[2-bromo-4-fluoro-6-(prop-1-enyl)phenoxy]but-3-enyl 4-methylbenzenesulfonate

Product 1

HCID 86609111(R)-(8-bromo-6-fluoro-2H-chromen-2-yl)methyl-4-methylbenzenesulfonateYield 101.3%

Reagents, catalysts & solvents 2

HCID 90332616Dichlororuthenium;tricyclohexyl-[phenyl-(tricyclohexyl-lambda5-phosphanyl)methyl]-lambda5-phosphaneCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of (R)-2-[2-bromo-4-fluoro-6-(prop-1-enyl)phenoxy]but-3-enyl 4-methylbenzenesulfonate (7.26 g, 0.016 mol) in dry dichloromethane (300 mL) at room temperature under nitrogen was added benzylidene-bis(tricyclohexylphosphine)-dichlororuthenium (2.6 g, 3.2 mmol) and the reaction mixture stirred at room temperature for 18 hours. The reaction mixture was then concentrated under reduced pressure to a small volume and directly pre-adsorbed onto silica gel. Purification by flash chromatography using a solvent gradient of 5 to 30% ethyl acetate in hexane gave 6.7 g (100%) of (R)-(8-bromo-6-fluoro-2H-chromen-2-yl)methyl-4-methylbenzenesulfonate as a grey solid. [α]D25=+206.6° (c 1% solution in MeOH); MS (ES) m/z 430.0 ([M+NH4]+).

Workup

  1. concentrationThe reaction mixture was then concentrated under reduced pressure to a small volume and directly pre-adsorbed onto silica gel
  2. customPurification by flash chromatography

Sources & evidence

ORD record
ord-89b609eb2dfc4b10beebe2e9e50bcb98
Source dataset
uspto-grants-2008_04
Patent number
US07365095B2

Reaction notes

Loading…