Recent progress towards ionic hydrogenation: Lewis acid catalyzed hydrogenation using organosilanes as donors of hydride ions

Abstract

Recent advances in ionic hydrogenation as well as its fundamental mechanism are summarized and discussed.

Highly Recyclable Fluoride for Enhanced Cascade Hydrosilylation–Cyclization of Levulinates to γ-Valerolactone at Low Temperatures

“…As a byproduct of the silicone industry and an attractive liquid H-donor, polymethylhydrosiloxane (PMHS) is insensitive to water/air, nontoxic to organisms, and inexpensive, which has drawn great attention in the ionic hydrogenation or hydrosilylation of unsaturated groups (e.g., CC, CO, and CN) catalyzed by metal hydrids, salts, or complexes. − Unfortunatedly, some practical drawbacks like poor catalyst reusability and the requirement of proton species or extra hydrolysis steps for the dissociation of Si–X (X = O, N, and S) bonds to liberate products are always encountered, especially for the selective hydrogenation of carbonyl compounds. , To the best of our knowledge, no effective approach has been reported to simplify the postprocess and further in situ couple the hydrosilylation with other reactions.…”

Auto‐Tandem Catalysis with Frustrated Lewis Pairs for Reductive Etherification of Aldehydes and Ketones

“…[8] Despite the wealth of ether linkage forming methodologies,t here is still ar oom for improvement in reaction efficiencya nd generality.R eductive etherification represents [9,10] an ideal methodology because this reaction can overcome many of the synthetic challenges of the venerable Williamson reaction [11] or acid-mediated dehydration processes. [8] Despite the wealth of ether linkage forming methodologies,t here is still ar oom for improvement in reaction efficiencya nd generality.R eductive etherification represents [9,10] an ideal methodology because this reaction can overcome many of the synthetic challenges of the venerable Williamson reaction [11] or acid-mediated dehydration processes.…”

Auto‐Tandem Catalysis with Frustrated Lewis Pairs for Reductive Etherification of Aldehydes and Ketones

“…Arguably one of the principal synthetic transformations in organic chemistry has been the construction of dialkyl ether linkage. [8] Despite the wealth of ether linkage forming methodologies,t here is still ar oom for improvement in reaction efficiencya nd generality.R eductive etherification represents [9,10] an ideal methodology because this reaction can overcome many of the synthetic challenges of the venerable Williamson reaction [11] or acid-mediated dehydration processes. [12] Although various silicon-and boron-based reducing agents have been used in reductive etherifications, [9] the application of amore atom-economic alternative,H 2 has not gained widespread utility because the employed precious metal catalysts have had limited functional group tolerance and protocols often necessitated harsh reaction conditions.…”