Recent Advances in the Hydrosilylation and Related Reactions

Abstract

Introduction Hydrosilylation of Alkenes Hydrosilylation of Alkynes Hydrosilylation of Carbonyl and Related Compounds Asymmetric Hydrosilylation Syntheses of Silicon‐Containing Dendrimers and Polymers Using Hydrosilylation Silylcarbonylation and Silylcarbocyclization Reactions

Soybean-Based Polyols and Silanols

“…This reaction has been used commercially as the major synthetic route to insert silanes to alkenes via a new Si-C bond formation. This hydrosilylation reaction where Si-H is inserted to alkenes has been widely investigated and reported in the literature (48)(49)(50). It can be carried out by free radical chain reactions or with various catalysts including platinum, palladium and other transition metal catalysts.…”

The Higher Propensity of Pd-SiHEt2+ over Pd-SiMe2Et+ to Transfer Silylium to Silyl Ether Intermediates Explains Divergent Products in Ketone Hydrosilylation Catalysis

“…Since Ojima's use of Wilkinson's catalyst, 1 numerous complexes have emerged as competent catalysts for the hydrosilylation of ketones, including ruthenium, rhodium-, iron-, and iridium-based systems. 2,3 Despite sharing similar M−SiR 3 intermediates, vastly different mechanisms have been reported across these systems. 4 Iron complexes typically activate silane by σ-bond metathesis across the Fe−OR bond, leading to metal-hydrides and silyl ether products (Scheme 1a).…”

“…The catalytic hydrosilylation of ketones through the intervention of metal-silyl complexes has yielded powerful methods for the synthesis of alcohols. Since Ojima’s use of Wilkinson’s catalyst, numerous complexes have emerged as competent catalysts for the hydrosilylation of ketones, including ruthenium, rhodium-, iron-, and iridium-based systems. , Despite sharing similar M–SiR 3 intermediates, vastly different mechanisms have been reported across these systems . Iron complexes typically activate silane by σ-bond metathesis across the Fe–OR bond, leading to metal-hydrides and silyl ether products (Scheme a). , Late metal species, especially rhodium catalysts, are thought to follow the mechanistic steps proposed by Ojima et al and are closely related to the Chalk–Harrod and modified Chalk–Harrod mechanisms. , Oxidative addition of hydrosilane followed by ketone coordination to rhodium allows for silyl transfer and subsequent C–H reductive elimination to yield product (Scheme b).…”

Enantioselective Synthesis of α‐Aminosilanes by Copper‐Catalyzed Hydroamination of Vinylsilanes

“…As vinylsilanes are readily prepared and bench-stable, they are attractive as starting materials for the synthesis of α-aminosilanes. [10] The intermolecular hydroamination of vinylsilanes would likely, based on literature precedent, proceed regioselectively to give chiral α-aminosilanes (III), via the α-silylalkylcopper intermediate II (Scheme 3), [11] on reaction with the O-benzoylhydroxylamine electrophile 2. [9] …”