Rh(I)-Catalyzed CO Gas-Free Carbonylative Cyclization Reactions of Alkynes with 2-Bromophenylboronic Acids Using Formaldehyde

Tsumoru Morimoto, Kae Yamasaki, Akihisa Hirano, Ken Tsutsumi, Natsuko Kagawa, Kiyomi Kakiuchi, Yasuyuki Harada, Yoshiya Fukumoto, Naoto Chatani, Takanori Nishioka

Organic Letters · 2009 · 142 citations · 33 references

Concepts

Abstract

The rhodium(I)-catalyzed reaction of alkynes with 2-bromophenylboronic acids in the presence of paraformaldehyde resulted in a CO gas-free carbonylative cyclization, yielding indenone derivatives. [RhCl(BINAP)](2) and [RhCl(cod)](2) were responsible for the decarbonylation of formaldehyde and the subsequent carbonylation of alkynes with 2-haloboronic acids, respectively, leading to efficient whole carbonylation. Sterically bulky and electron-withdrawing groups on unsymmetrically substituted alkynes favored the alpha-position of indenones.

References

33