Programmable Ether Synthesis Enabled by Oxa-Matteson Reaction

The Matteson-type reactions have received increasing interest in constructing complex organic molecules via iterativesynthetic strategies; however, the current tactics are almost exclusively based on homologation of pure carbon chains. Here, wereport the development of the oxa-Matteson reaction that enables sequential oxygen and carbenoid insertions into diverse alkyl- andarylboronates. It offers a distinct entry to a wide range of boron-substituted ethers. The utilities of this method are demonstrated inthe preparation of various functional ethers, the asymmetric synthesis of an acetyl-CoA-carboxylase inhibitor, and the programmableconstruction of polyethers.

Automated summary

The Matteson-type reactions have gained increasing interest in organic synthesis, but current tactics mainly focus on carbon chains. In this study, we report the development of the oxa-Matteson reaction, which allows oxygen and carbenoid insertions into alkyl- and arylboronates, leading to the synthesis of boron-substituted ethers. The method demonstrates its utility in the preparation of functional ethers, asymmetric synthesis, and programmable construction of polyethers.