Manganese‐Catalyzed Hydrosilylation Reactions

Abstract

Over the past few decades, manganese-catalyzed hydrosilylation of C=O or C=C/C≡C unsaturated bonds have undergone enormous developments. In this focus review, the hydrosilylation reactions of alkenes, alkynes, and carbonyl-containing substrates catalyzed by manganese complexes are summarized. Moreover, the mechanisms of the manganese-catalyzed hydrosilylation are briefly discussed.

Generation and Reactivity of Amidyl Radicals: Manganese‐Mediated Atom‐Transfer Reaction

“…As the twelfth most abundant element and the third most abundant transition metal after iron and titanium, manganese has been successfully exploited as a low‐toxicity and low‐cost catalyst for a variety of practical transformations . Manganese‐catalyzed C−H oxidations, halogenations, nitrogenations, cross‐couplings, hydrosilylations, and C−H activations have been intensively investigated in the past decades. In stark contrast, manganese‐catalyzed atom‐transfer reactions for generating radical species have received less attention.…”

A Manganese N‐Heterocyclic Carbene Catalyst for Reduction of Sulfoxides with Silanes

“…In fact, the development of manganese catalysis has experienced a spectacular growth in the last few years . In particular, manganese‐mediated hydrosilylation reactions have proved to be a convenient method for the reduction of carbonyl groups, including aldehydes and ketones, esters, amides, carboxylic acids, CO 2 , and C=C/C≡unsaturated bonds . Last year, we disclosed the excellent reactivity of Mn(I) complexes supported by bidentate NHC ligands (NHC=N‐heterocyclic carbene) in the catalytic reduction of carbonyl groups .…”

“…[7] Last year, we disclosed the excellent reactivity of Mn(I) complexes supported by bidentate NHC ligands (NHC=Nheterocyclic carbene) in the catalytic reduction of carbonyl groups. [8,9] Motivated by these findings, we became interested in further exploring the potential of [Mn(bis-NHC)(CO) 3 Br] complexes in reductions with silanes. Surprisingly, despite the enormous success of metal NHC complexes in catalysis, [10] very few catalytic applications of Mn-NHC complexes can be found in the literature.…”

“…Surprisingly, despite the enormous success of metal NHC complexes in catalysis, [10] very few catalytic applications of Mn-NHC complexes can be found in the literature. [4f,g,8,9,11,12] We report in this work the deoxygenation of sulfoxides to sulfides with silanes mediated by the manganese complex [Mn(bis-NHC)(CO) 3 Br] bearing a bis-Nheterocyclic carbene ligand. The deoxygenation of sulfurcontaining compounds is a fundamental reaction in organic synthesis and biochemistry.…”

External Electric Field—Phenyl interaction boosts hydrosilylation of substituted alkynes to α‐vinylsilane

“…Vinylsilanes are valuable building blocks in organic synthesis and material chemistry because of their versatile characters, such as low toxicity, high stability, facile manipulations, and a variety of transformations . Accordingly, methods for the preparation of vinylsilanes have gained increased attentions from synthetic chemists, in which the hydrosilylation of alkynes was considered as a simple and straightforward method . This hydrosilylation reaction involves the addition of a Si − H bond across a C − C triple bond, bringing an atom‐economical result with 100% atom efficiency.…”