Methanol → 2-(4-isopropyl-4H-[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-8-carboxylic acid methyl ester

https://huagongshe.com/reaction/1190272

Participants

Role	Name	HCID	Charge
Reactant	Methanol	HCID 887	—
Reactant	1,4-Dioxane	HCID 31275	—
Reactant	1,8-Diazabicyclo(5.4.0)undec-7-ene	HCID 81184	—
Reactant	Tri-tert-butylphosphine tetrafluoroborate	HCID 2734635	—
Reactant	8-Bromo-2-(4-isopropyl-4H-[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene	HCID 58203806	—
Catalyst	Molybdenum carbonyl (Mo(CO)6)	HCID 98885	—
Catalyst	trans-Bis(acetato)bis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium(II)	HCID 11104995	—
Product	2-(4-isopropyl-4H-[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-8-carboxylic acid methyl ester	HCID 58204037	54%

Reaction Conditions

Temperature	150 °C

Reaction Steps

A microwave vial was charged with 8-bromo-2-(4-isopropyl-4H[1,2,4]triazol-3-yl)-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene (1.0 g, 2.56 mmol), molybdenum hexacarbonyl (338 mg, 1.28 mmol), Herrmann's catalyst [trans-bis(acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II)] (122 mg, 0.13 mmol), tri-tert-butylphosphonium tetrafluoroborate (75 mg, 0.26 mmol), DBU (0.38 mL, 2.56 mmol), 1,4-dioxan (6 mL) and MeOH (6 mL), flushed with nitrogen then sealed. The mixture was heated at 150° C. for 45 minutes using microwave irradiation then filtered through a pad of Celite®, washing the pad with MeOH. The filtrate was concentrated in vacuo and the residue purified by flash chromatography (SiO2, 0-5% MeOH in EtOAc) to give the title compound as a yellow solid (0.51 g, 54%). LCMS: RT=4.28 min, [M+H]+=371

Provenance & Evidence

DOI	10.6084/m9.figshare.5104873.v1
Patent number	US08673952B2
Source dataset	uspto-grants-2014_03
ORD ID	ord-636d851cf88b4110ab1d7ce23ce70140
Source note	uspto-grants-2014_03