Practical and Selective Bio-Inspired Iron-Catalyzed Oxidation of Si-H Bonds to Diversely Functionalized Organosilanols

Functionalized organosilanols have found wide applications pervading the realms of chemistry, material science, and medicine. However, a practical synthesis of structurally diverse organosilanols has remained elusive. Here, a bio-inspired nonheme-iron-catalyzed preparative oxidation of Si-H bonds of organo-silanes to diversely functionalized organosilanols with aqueous hydrogen peroxide as the oxidant at an iron catalyst loading of 0.1 mol % is reported. The practical and highly selective oxidation exhibits good functional group tolerance, allowing effective access to diversely functionalized alkyl-, aryl-, alkynyl-, and alkoxysilanols, silanediols, as well as mono-, oligo-, and polymeric siloxanols with various substituent patterns. Late-stage gram-scale application in functional-molecule-containing silanols is further demonstrated. Mechanistic studies suggest the involvement of high-valent Fe(V)oxo species and a sequence of hydrogen atom transfer and oxygen rebounds.

Automated summary

This study reports a bio-inspired nonheme-iron-catalyzed method for the efficient and selective preparation of diversely functionalized organosilanols. The practical method allows for the synthesis of organosilanols with different substituent patterns and exhibits good functional group tolerance. The study also demonstrates the potential application of this method in the synthesis of functional molecules containing silanols.