Iron‐catalyzed hydrosilylation reactions

Abstract

Iron-catalyzed hydrosilylation is one of the most popular reduction reactions owing to the high natural abundance, low cost and low toxicity of iron and silicon. This paper introduces an advance in iron-catalyzed hydrosilylation of olefins, aldehydes, ketones and amides. Some reactions exhibit good functional group tolerance and chemoselectivities. These protocols provide economical, sustainable and practical tools for organic chemists.

Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications

“…The reaction proceeded even with non-activated chlorides such as methyldichlorosilane, which was not feasible under Benkeser reaction conditions, in which stoichiometric amounts of amines are required as hydrochloride scavangers. Using Bu 4 PCl, Jung et al obtained the highest yields and conversions. Quantitative conversions of various benzyl chlorides with HSiCl 3 were achieved at 130 • C within 4 h. Quarternary organoammonium chlorides were much less effective catalysts; non-activated alkyl chlorides together with ammonium catalyst failed to catalyze the product formation.…”

“…The as-formed intermediate can attack the alkyl chloride, achieve Si-C coupling, and regenerate the catalyst. Yoo and coworkers employed Bu 4 PCl for reactions wit HSiCl 3 affording bis(chlorosilyl)methanes in moderate yields (up to 70%) [50]. Pike reported the addition of trichlorosilane to hydrocarbon olefins, catalyzed by tertiary amine and tertiary phosphine compounds (loads of 4-6 mol %) [48].…”

“…Hydrosilylation reactions catalyzed by platinum catalysts commonly follow Chalk-Harrod and modified Chalk-Harrod mechanisms (Figure 3), rendering side-reactions possible that yield unfavorable by-products and, correspondingly, lower the yield of the targeted product(s) and increase the production costs. Due to research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since Polymers 2017, 9, 534 2 of 37 research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively.…”

“…Due to research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since Polymers 2017, 9, 534 2 of 37 research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively.…”

“…1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since Polymers 2017, 9, 534 2 of 37 research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since research for alternative platinum-free catalysts containing low-cost-transition metals and/or metalorganic compounds [4,5] is performed extensively. 1968 1972 1976 1980 1984 1988 1992 1996 Due to the increasing demand for silanes and siloxanes by industrial manufacturers, novel hydrosilylation methods [6,7] have been in the focus of research over the last years, particularly since An iron-disilyl-dicarbonyl complex carrying a 1,2-bis(dimethylsilyl)benzyl ligand that (weakly) coordinated to the iron center in η 2 -(H-Si) was reported by Nagashima and coworkers [15].…”