Organic silicon compounds, critical in materials science and pharmaceutical development, serve as cornerstones of modern industries due to their unique chemical stability and structural diversity. However, these compounds do not occur naturally and must be synthesized chemically.

In traditional processes, the stepwise substitution reaction starting from silicon tetrachloride (SiCl₄) represents one of the simplest direct synthesis routes but suffers from chemoselectivity issues caused by over-substitution.

In addressing this, Professor Wang Youliang's team at Xi'an Jiaotong University (XJTU) achieved the first controlled stepwise ligation of four distinct alcohol molecules onto a single silicon atom, synthesizing siliconanes with four different alkoxy groups – structures difficult to obtain via conventional methods.

The team employed triphenylchlorosilane (Ph₃SiCl) as a synthetic equivalent of SiCl₄, using dephenylative etherification as the key reaction. This enabled precise cleavage of silicon-phenyl bonds by electrophilic halogenation reagents and controlled connection of alcohol molecules.

The ligation technique demonstrates broad substrate adaptability: structurally diverse primary, secondary, and tertiary alcohols – from sterically hindered perfluoro-tert-butanol to bioactive menthol – participate effectively.

Water transitions from a reaction obstacle to the preferred solvent, marking the first aqueous silyl ether protection of hydroxyl groups. This breakthrough eliminates the stringent anhydrous requirements typically associated with chlorosilane-based hydroxyl protection.

This research, titled Single-Atom Ligation of Four Different Alcohols at One Silicon Center: Methodology Development and Proof of Concept, was published in Angewandte Chemie International Edition.