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, Kazuhiko Takai

Research output: Contribution to journalArticle

7 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)1491-1501
Number of pages11
JournalPure and Applied Chemistry
Volume82
Issue number7
DOIs
Publication statusPublished - 2010

Fingerprint

Rhenium
Alkynes
Manganese
Esters
Carbon
Benzene
Aromatic compounds
Molecular sieves
Cyanides
Carbon Monoxide
Carbon Dioxide
Carbon dioxide
Catalysts

Keywords

  • 1,3-dicarbonyl
  • Alkyne
  • Carbon-carbon bond formation
  • Insertion
  • Manganese
  • Organic synthesis
  • Rhenium
  • Ring enlargement
  • Substituted benzene

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Rhenium- and manganese-catalyzed carbon-carbon bond formation using 1,3-dicarbonyl compounds and alkynes. / Kuninobu, Yoichiro; Kawata, Atsushi; Yudha, Salprima S.; Takata, Hisatsugu; Nishi, Mitsumi; Takai, Kazuhiko.

In: Pure and Applied Chemistry, Vol. 82, No. 7, 2010, p. 1491-1501.

Research output: Contribution to journalArticle

Kuninobu, Yoichiro ; Kawata, Atsushi ; Yudha, Salprima S. ; Takata, Hisatsugu ; Nishi, Mitsumi ; Takai, Kazuhiko. / Rhenium- and manganese-catalyzed carbon-carbon bond formation using 1,3-dicarbonyl compounds and alkynes. In: Pure and Applied Chemistry. 2010 ; Vol. 82, No. 7. pp. 1491-1501.
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