1‐Hydrosilatrane: A Locomotive for Efficient Ketone Reductions

Abstract

An efficient method for the reduction of ketones with 1‐hydrosilatrane is described. In the presence of a Lewis base activator, the resulting secondary alcohols are rapidly formed in good to excellent yields (20 examples, 71–99 % yields). The relative bulkiness of 1‐hydrosilatrane also enables the diastereoselective reduction of (–)‐menthone to (+)‐neomenthol, and the use of a chiral alkoxide activator can lead to the enantioselective reduction of prochiral ketones.

One-Pot Reductive Acetylation of Aldehydes using 1-Hydrosilatrane in Acetic Acid

“…22 1-Hydrosilatrane is an attractive reducing agent because it is air-and moisture-stable, inexpensive, and simple to synthesize. 21 While most of our work has shown silatrane reduction utilizing a Lewis base activator, experimental observations indicate that weak Brønsted acids also facilitate the reduction of aldehydes with no observed ether formation. With this in mind, this work seeks to expand the utility of silatrane by developing a simple and efficient way of synthesizing esters from aldehydes in a single-pot reaction (Scheme 1c) and reports our findings to date towards this aim.…”

“…Recently, our group has developed several reductive methods using 1-hydrosilatrane ( Figure 1). Our research program has led to the development of a direct route for the reduction of aldehydes and ketones to their corresponding alcohols 20,21 and direct reductive aminations of aldehydes and ketones in the presence of an amine. 22 1-Hydrosilatrane is an attractive reducing agent because it is air-and moisture-stable, inexpensive, and simple to synthesize.…”

Hydrosilylation and hydroboration in a sustainable manner: from Earth-abundant catalysts to catalyst-free solutions

“…3). 75,76 This is a very interesting alternative to simple hydrosilanes. 1-Hydrosilatrane is very expensive in the commercial market, but it might be individually synthesized from cheap and easily accessible reagents, and finally, it can be stored for several months without any special handling.…”

Reactivity of 1-allylsilatrane in ruthenium-catalyzed silylative coupling with olefins – mechanistic considerations

“…Silatranes make a widely studied class of organosilicon compounds characterized by cage tricyclic structure, pentacoordinate silicon center with donor-acceptor transannular Si ← N bond, and interesting biological properties [1][2][3]. In the last three decades, research on silatranes covered several areas, including organic and organometallic synthesis [4][5][6], materials chemistry [7][8][9] as well as biochemistry and medicine [10][11][12][13] Given the variety of silatrane derivatives, allylsilatranes are hardly explored, which stands in stark contrast to the wide range of applications of allylsilanes in organic synthesis (e.g., in allylation of carbonyl compounds or olefin metathesis, for review see [14]). 1-Allylsilatrane (or allylsilatrane) 1 is the simplest representative of allylsubstituted silatranes (Figure 1).…”