Rhenium- and manganese-catalyzed carbon&ndash;carbon bond formation using 1,3‑dicarbonyl compounds and alkynes

Kuninobu, Yoichiro; Kawata, Atsushi; Yudha, Salprima S.; Takata, Hisatsugu; Nishi, Mitsumi; Takai, Kazuhiko

doi:10.1351/PAC-CON-09-09-21

Pure Appl. Chem., 2010, Vol. 82, No. 7, pp. 1491-1501

http://dx.doi.org/10.1351/PAC-CON-09-09-21

Published online 2010-05-06

Rhenium- and manganese-catalyzed carbon–carbon bond formation using 1,3‑dicarbonyl compounds and alkynes

Yoichiro Kuninobu*, Atsushi Kawata, Salprima S. Yudha, Hisatsugu Takata, Mitsumi Nishi and Kazuhiko Takai*

Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Kita-ku, Okayama 700-8530, Japan

Abstract: A rhenium complex, [ReBr(CO)₃(thf)]₂, catalyzed insertion of terminal alkynes into a C–H bond of active methylene sites of 1,3-dicarbonyl compounds. When a catalytic amount of isocyanide or molecular sieves was added to the reaction mixture, the reaction course changed markedly, and insertion of alkynes into a C–C single bond between α- and β-positions of cyclic and acyclic β-keto esters occurred. The formed acyclic δ-keto esters could be converted to 2-pyranones, which were applied to the synthesis of multisubstituted aromatic compounds via the Diels–Alder reaction and successive elimination of carbon dioxide. In the case of the rhenium-catalyzed reactions between terminal alkynes and β-keto esters without substituent at the α-position, tetrasubstituted benzenes were produced regioselectively by two-to-one reaction of the components. The yields of tetrasubstituted benzenes were improved by using a manganese catalyst.