Selective Rhodium-Catalyzed Hydroformylation of Terminal Arylalkynes and Conjugated Enynes to (Poly)enals Enabled by a π-Acceptor Biphosphoramidite Ligand

The hydroformylation of terminal arylalkynes and enynes offers a straightforward synthetic route to the valuable (poly)enals. However, the hydroformylation of terminal alkynes has remained a long-standing challenge. Herein, an efficient and selective Rh-catalyzed hydroformylation of terminal arylalkynes and conjugated enynes has been achieved by using a new stable biphosphoramidite ligand with strong pi-acceptor capacity, which affords various important E-(poly)enals in good yields with excellent chemo- and regioselectivity at low temperatures and low syngas pressures.

Automated summary

A new stable biphosphoramidite ligand with strong pi-acceptor capacity has enabled an efficient and selective Rh-catalyzed hydroformylation of terminal arylalkynes and conjugated enynes. This method allows the synthesis of various important E-(poly)enals in good yields with excellent chemo- and regioselectivity at low temperatures and low syngas pressures.