The development of efficient Si–O bond formation reaction with 100% atom-economy, excellent functional group tolerance, and broad scope under mild conditions is highly desired due to the prevalence of silanol, silyl ether, and their derivatives in synthetic chemistry and materials science. Here, we have realized the Pd-catalyzed Si–O formation reaction via a Si–C activation approach with 100% atom-economy by employing silacyclobutanes (SCBs) and various hydroxy-containing substrates, including water, alcohols, phenols, and silanols. This protocol features a broad substrate scope, remarkable functional compatibility and mild conditions, providing a series of silanols, silyl ethers in high efficiency. Notably, this protocol could also be used for selective protection of hydroxy functionalities, and for the access of a class of novel polymers containing Si–O main chain. Preliminary mechanistic studies unveiled that this reaction underwent a Pd-catalyzed concerted ring-opening mechanism.

由于硅烷醇、甲硅烷基醚及其衍生物在合成化学和材料科学中的普遍存在，非常需要开发具有 100% 原子经济性、优异的官能团耐受性和温和条件下广泛范围的高效 Si-O 键形成反应。 。在这里，我们使用硅杂环丁烷（SCB）和各种含羟基底物（包括水、醇、酚和硅烷醇），通过 Si-C 活化方法实现了 Pd 催化的 Si-O 形成反应，具有 100% 原子经济性。该方案具有底物范围广、功能相容性好、条件温和等特点，能够高效地提供一系列硅烷醇、硅醚。值得注意的是，该方案还可用于选择性保护羟基官能团，以及获取一类含有 Si-O 主链的新型聚合物。初步机理研究表明，该反应经历了钯催化的协同开环机制。