Rhodium-Catalyzed Cross-Cyclotrimerization and Dimerization of Allenes with Alkynes

Kazuki Sakashita; Yu Shibata; Ken Tanaka

doi:10.1002/anie.201602155

Rhodium-Catalyzed Cross-Cyclotrimerization and Dimerization of Allenes with Alkynes

Angew Chem Int Ed Engl. 2016 Jun 1;55(23):6753-7. doi: 10.1002/anie.201602155. Epub 2016 Apr 25.

Authors

Kazuki Sakashita^{1

2}, Yu Shibata¹, Ken Tanaka^{3

4}

Affiliations

¹ Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.
² Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo, 184-8588, Japan.
³ Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan. ktanaka@apc.titech.ac.jp.
⁴ Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo, 184-8588, Japan. ktanaka@apc.titech.ac.jp.

PMID: 27110668
DOI: 10.1002/anie.201602155

Abstract

It has been established that a cationic rhodium(I)/binap complex catalyzes the cross-cyclotrimerization of two molecules of a monosubstituted allene with one molecule of a functionalized alkyne to give 3,6-dialkylidenecyclohex-1-enes. In contrast, the reactions involving di- or trisubstituted allenes and/or unfunctionalized alkynes afforded cross-dimerization products, substituted dendralenes, through β-hydrogen elimination from the corresponding rhodacycles.

Keywords: alkynes; allenes; cyclization; dimerization; rhodium.

Publication types

Research Support, Non-U.S. Gov't