Catalytic Synthesis of Silanols by Hydroxylation of Hydrosilanes: From Chemoselectivity to Enantioselectivity

Abstract

As a crucial class of functional molecules in organosilicon chemistry, silanols are found valuable applications in the fields of modern science and will be a potentially powerful framework for biologically active compounds or functional materials. It has witnessed an increasing demand for non‐natural organosilanols, as well as the progress in the synthesis of these structural features. From the classic preparative methods to the catalytic selective oxidation of hydrosilanes, electrochemical hydrolysis of hydrosilanes, and then the construction of the most challenging silicon‐stereogenic silanols. This review summarized the progress in the catalyzed synthesis of silanols via hydroxylation of hydrosilanes in the last decade, with a particular emphasis on the latest elegant developments in the desymmetrization strategy for the enantioselective synthesis of silicon‐stereogenic silanols from dihydrosilanes.

X-type silyl ligands for transition-metal catalysis

“…In recent years, transition-metal-catalyzed dehydrogenative Si–O coupling has emerged as a powerful approach for the production of silanols and siloxanes due to its atom economy and high efficiency. 178,179 In this section, a brief overview of dehydrogenative Si–O coupling reactions catalyzed by silyl metal complexes is provided, and the recent catalytic asymmetric methods using chiral silyl ligands are also discussed.…”

Electrochemical strategies for NaX-mediated hydrolysis and alcoholysis of hydrosilanes under mild conditions

“…6 As a direct consequence, the fundamental importance of silanols has given a great impetus to developing versatile methods for the synthesis of silanols in the realms of synthetic chemistry. 7…”