Rhodium(III)-Catalyzed Tandem [2+2+2] Annulation-Lactamization of Anilides with Two Alkynoates via Cleavage of Two Adjacent C-H or C-H/C-O bonds

Miho Fukui; Yu Shibata; Yuki Hoshino; Haruki Sugiyama; Kota Teraoka; Hidehiro Uekusa; Keiichi Noguchi; Ken Tanaka

doi:10.1002/asia.201600943

Rhodium(III)-Catalyzed Tandem [2+2+2] Annulation-Lactamization of Anilides with Two Alkynoates via Cleavage of Two Adjacent C-H or C-H/C-O bonds

Chem Asian J. 2016 Aug 19;11(16):2260-4. doi: 10.1002/asia.201600943. Epub 2016 Aug 9.

Authors

Miho Fukui^{1

2}, Yu Shibata³, Yuki Hoshino², Haruki Sugiyama⁴, Kota Teraoka⁴, Hidehiro Uekusa⁴, Keiichi Noguchi⁵, Ken Tanaka^{6

7}

Affiliations

¹ Department of Chemical 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 Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan. yshibata@apc.titech.ac.jp.
⁴ Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.
⁵ Instrumentation Analysis Center, Tokyo University of Agriculture and Technology, Koganei, Tokyo, 184-8588, Japan.
⁶ Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan. ktanaka@apc.titech.ac.jp.
⁷ 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: 27412046
DOI: 10.1002/asia.201600943

Abstract

An electron-deficient Cp(E) rhodium(III) complex bearing a cyclopentadienyl ligand with two ethyl ester substituents catalyzes the tandem [2+2+2] annulation-lactamization of acetanilides with two alkynoates via cleavage of adjacent two C-H bonds to give densely substituted benzo[cd]indolones. The reactions of meta-methoxy-substituted acetanilides with two alkynoates also provided benzo[cd]indolones via cleavage of adjacent C-H/C-O bonds. Furthermore, 3,5-dimethoxyacetanilides reacted with two alkynoates to give dearomatized spiro compounds.

Keywords: alkynes; anilides; annulation; benzo[cd]indolones; rhodium.