A highly selective palladium-catalyzed carbonylation of 2-alkynylanilines bearing an amide moiety to condensed six-membered heterocyclic structures has been developed under mild conditions(room temperature and atmosph...A highly selective palladium-catalyzed carbonylation of 2-alkynylanilines bearing an amide moiety to condensed six-membered heterocyclic structures has been developed under mild conditions(room temperature and atmospheric pressure of CO).The carbonylative protocol is also compatible with CO surrogates,such as benzene-1,3,5-triyl triformate(TFBen)or the newly developed calix[6]arenes functionalized with six formate groups(CLX[6]CO),which are both capable to release CO in situ.A series of tricyclic fused heterocycles containing the important oxazino-quinolinone scaffold have been selectively obtained(only the 6-endo-dig cyclization mode has been observed)in good to excellent yields(up to 99%).展开更多
The PdI_(2)/KI-catalyzed oxidative carbonylation of 4-(2-aminophenyl)-3-yn-1-ols,bearing two potential nucleophilic groups in suitable position selectively leads to dihydrofuroquinolinone derivatives in fair to high y...The PdI_(2)/KI-catalyzed oxidative carbonylation of 4-(2-aminophenyl)-3-yn-1-ols,bearing two potential nucleophilic groups in suitable position selectively leads to dihydrofuroquinolinone derivatives in fair to high yields(60%—89%)and excellent turnover numbers(180—267 mol of product per mol of Pd)over 19 examples,through a mechanistic pathway involving initial O-cyclization followed by N-cyclocarbonylation.In such process,the selective catalytic construction of two rings and three new bonds is achieved in one synthetic step to afford high value added fused heterocyclic structures starting from readily available materials.展开更多
基金from the equipment and framework of the COMP-HUB Initiative,funded by the“Departments of Excellence"program of the Italian Ministry for Education,University and Research(MIUR,2018-2022)"ECOSISTER"funded under the National Recovery and Resilience Plan(NRRP),Mission 04 Component 2 Investment 1.5-NextGenerationEU(Call for tender n.3277,30/12/2021Award Number 0001052,dated 23/06/2022).
文摘A highly selective palladium-catalyzed carbonylation of 2-alkynylanilines bearing an amide moiety to condensed six-membered heterocyclic structures has been developed under mild conditions(room temperature and atmospheric pressure of CO).The carbonylative protocol is also compatible with CO surrogates,such as benzene-1,3,5-triyl triformate(TFBen)or the newly developed calix[6]arenes functionalized with six formate groups(CLX[6]CO),which are both capable to release CO in situ.A series of tricyclic fused heterocycles containing the important oxazino-quinolinone scaffold have been selectively obtained(only the 6-endo-dig cyclization mode has been observed)in good to excellent yields(up to 99%).
文摘The PdI_(2)/KI-catalyzed oxidative carbonylation of 4-(2-aminophenyl)-3-yn-1-ols,bearing two potential nucleophilic groups in suitable position selectively leads to dihydrofuroquinolinone derivatives in fair to high yields(60%—89%)and excellent turnover numbers(180—267 mol of product per mol of Pd)over 19 examples,through a mechanistic pathway involving initial O-cyclization followed by N-cyclocarbonylation.In such process,the selective catalytic construction of two rings and three new bonds is achieved in one synthetic step to afford high value added fused heterocyclic structures starting from readily available materials.
