4-Methoxy-alpha-toluenethiol → 3-Fluoro-5-(4-methoxy-benzylsulfanyl)-benzoic acid ethyl ester

Participants

Role	Name	HCID	Charge
Reactant	4-Methoxy-alpha-toluenethiol	HCID 80407	—
Reactant	Diisopropylethylamine	HCID 81531	—
Reactant	1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)	HCID 636044	—
Reactant	Ethyl 3-Bromo-5-fluorobenzoate	HCID 43476807	—
Catalyst	Bis(dibenzylideneacetone)palladium	HCID 9811564	—
Solvent	1,4-Dioxane	HCID 31275	—
Product	3-Fluoro-5-(4-methoxy-benzylsulfanyl)-benzoic acid ethyl ester	HCID 66765059	—

Reaction Conditions

Temperature	90 °C

Reaction Steps

To a room temperature, degassed solution of 3-Bromo-5-fluoro-benzoic acid ethyl ester (4.0 g, 16.2 mmol) in dioxane (100 mL) was added 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.48 g, 0.82 mmol), 4-methoxy-benzylmercaptan (2.26 mL, 16.2 mmol), DIEA (5.6 mL, 32.4 mmol), and tris(dibenzylideneacetone)dipalladium(0) (0.37 g, 0.41 mmol). The resulting mixture was warmed to 90° C. and stirred for 2 hrs, then cooled to room temperature. The mixture was subjected to standard aqueous workup, and the crude residue was filtered through a pad of silica gel to afford the title compound.

Provenance & Evidence

DOI	10.6084/m9.figshare.5104873.v1
Patent number	US09000025B2
Source dataset	uspto-grants-2015_04
ORD ID	ord-45e8d9b22f70431bad99d4a81f6b0988
Source note	uspto-grants-2015_04