Programmable Ether Synthesis Enabled by Oxa-Matteson Reaction.

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

马特森型反应通过迭代合成策略构建复杂有机分子受到了越来越多的关注；然而，目前的策略几乎完全基于纯碳链的同系化。在此，我们报道了氧杂 - 马特森反应的发展，该反应能够将氧和类卡宾依次插入到各种烷基 - 和芳基硼酸酯中。它为广泛的硼取代醚提供了一种独特的合成途径。这种方法的实用性在各种功能性醚的制备、乙酰辅酶A羧化酶抑制剂的不对称合成以及聚醚的可编程构建中得到了证明。