Ethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-bromo-3-(6-phenylpyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)-1-methylcyclohex-3-enecarboxylate → (Z)-ethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-(2-ethoxyvinyl)-3-(6-phenylpyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)-1-methylcyclohex-3-enecarboxylate

Participants

Reaction Conditions

Reaction Steps

A mixture of ethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-bromo-3-(6-phenylpyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)-1-methylcyclohex-3-enecarboxylate (Int-18g, 48 mg, 0.061 mmol), (Z)-1-ethoxy-2-(tributylstannyl)ethane (72 mg), Pd(PPh3)4 (11 mg, 0.01 mmol) in dioxane (3 ml) was stirred at 100° C. under Ar for 8 h. After cooling to rt, the reaction mixture was passed through a short SiO2/KF (9:1) plug to removed majority of the Sn species. The filtrate was concentrated to give (Z)-ethyl 4-(7-(bis((2-(trimethylsilyl)ethoxy)methyl)amino)-6-(2-ethoxyvinyl)-3-(6-phenylpyridin-3-yl)pyrazolo[1,5-a]pyrimidin-5-yl)-1-methylcyclohex-3-enecarboxylate (Int-18h) which was used in the next step directly without further purification. HPLC-MS tR=3.02 min (UV254 nm); mass calculated for formula C43H61N5O5Si2 783.4, observed LCMS m/z 784.2 (M+H).

Provenance & Evidence