New method for preparation of coumarins and quinolinones via Pd-catalyzed intramolecular hydroarylation of C-C triple bonds.
A new and general method has been developed for preparation of coumarins and quinolinones by intramolecular hydroarylation of alkynes. Various aryl alkynoates and alkynanilides undergo fast intramolecular reaction at room temperature in the presence of a catalytic amount of Pd(OAc)(2) in a mixed solvent containing trifluoroacetic acid (TFA), affording coumarins and quinolinones in moderate to excellent yields with more than 1000 turnover numbers (TON) to Pd. The methodology proved to tolerate a number of functional groups such as Br and CHO. On the basis of isotope experiments, a possible mechanism involving ethynyl chelation-assisted electrophilic metalation of aromatic C-H bonds by in-situ generated cationic Pd(II) species has been discussed. Also the involvement of vinylcationic species has been suggested.
Jia
C
C
Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Hakozaki, Fukuoka, 812-8581, Japan. yfujitcf@mbox.nc.kyushu-u.ac.jp
Piao
D
D
Kitamura
T
T
Fujiwara
Y
Y
D002384:Catalysis; D003374:Coumarins / Q000138:chemical synthesis*; D003500:Cyclization; D007202:Indicators and Reagents; D010165:Palladium / Q000737:chemistry; D011804:Quinolines / Q000138:chemical synthesis*
D003374:Coumarins; D007202:Indicators and Reagents; D011804:Quinolines; D010165:Palladium