Synthesis of Diversely Functionalized 2 H-Chromenes through Pd-Catalyzed Cascade Reactions of 1,1-Dibromoolefin Derivatives with Arylboronic Acids.

Abstract

In this work, an unprecedented synthesis of (2 H-chromen-2-ylidene)acetates and (2 H-chromen-2-ylidene)ethanones with controlled stereoselectivity via Pd-catalyzed cascade reactions of 3-(2-(2,2-dibromovinyl)phenoxy)acrylates or 3-(2-(2,2-dibromovinyl)phenoxy)enones with aryl boronic acids has been established. This protocol combines two C-C bond forming reactions (an intermolecular Suzuki coupling followed by an intramolecular Heck coupling) in one pot under the catalysis of the same catalyst. Compared with literature methods for the preparation of 2 H-chromene derivatives, it has advantages such as easily obtainable or commercially available substrates, diverse substitution pattern of products, simple procedure, and excellent stereoselectivity. Interestingly, this cascade reaction could distinguish the subtle difference of the electron-withdrawing capacity and the size of various functional groups and thus resulted in a different chemoselectivity. In addition, the utility of the (2 H-chromen-2-ylidene)acetate thus obtained was showcased by its facile transformation into the synthetically and photophysically significant 3 H-xanthen-3-one derivative.