Manganese-catalyzed dehydrogenative coupling of silanes and hydroxyl compound controlled by phosphine oxide
Tao Li, Hong Zhang, Albert S. C. Chan, Shan‐Shui Meng
Abstract
Dehydrogenative coupling of silanes and hydroxyl compounds is a useful method for accessing compounds containing an Si–O bond. Alongside previous advances, practical and large-scale dehydrogenative coupling catalyzed by an available and cheap catalytic system remains appealing. Here, we report a general dimanganese decacarbonyl-catalyzed dehydrogenative coupling of silanes and hydroxyl compounds with inexpensive phosphine oxide ligands. This dehydrogenative coupling features a broad substrate scope of hydroxyl compounds, producing the corresponding silyl ethers and silanols in moderate to high yields (>91 examples, up to 99% yield). N-silylated indoles are also successfully synthesized by direct dehydrogenative coupling of N–H bonds and silanes. This reaction can be achieved on a 40 g scale with only 2.5 mol % of the manganese catalyst, delivering the desired silyl ether in a quantitative yield without any isolation difficulties. In exploration of the mechanism, we find a probable and uncommon organometallic pathway controlled by the phosphine oxide ligand.