Iron, Cobalt and Nickel Catalyzed Hydrosilylative Reduction of Functional Groups

: Hydrosilylation is an important transformation in organic synthesis. It has displayed widespread applications in homogenous catalysis and in the commercial production of organosilanes and organosilicon compounds. Though metals like Ru, Rh etc were used widely for achieving hydrosilylation, the increasing environmental concerns and the search for less expensive alternatives resulted in the investigation of transition metals. Metals like Ni, Co etc exhibit potential cost benefits, in addition to their low CO2 foot print and lower toxicity. Thus, transition metal catalysis has emerged as a promising strategy for hydrosilylation. This comprehensive review discusses the catalytic hydrosilylation of various functional groups with non-noble transition metals such as iron, cobalt and nickel in the last decade. Here, the topic is categorized based on the substrate functional groups such as aldehydes, ketones, alkenes, etc.

A Glimpse and Perspective of Current Organosilicon Chemistry from the View of Hydrosilylation and Synthesis of Silicon-Stereogenic Silanes

Silicon and its related organosilicon chemistry has become a mainstay in synthetic chemistry as they can participate in numerous organic transformations. Due to space limitations, this perspective is focused on a glimpse of current organosilicon chemistry from the view of catalytic hydrosilylation and synthesis of silicon-stereogenic silanes. The progress of the two topics fully illustrates that organosilicon chemistry has become a hot research field in recent years and will play a greater role in academic research and industrial applications of silicon element in the future.1 Introduction2 Hydrosilylation3 Catalytic Constructions of Silicon-Stereogenic Centers4 Conclusion and Perspective

Carboxylate-Functionalized P, N-Ligated Cobalt Catalysts for Alkene Hydrosilylation

: A series of N, P-ligands bearing carboxyl groups has been synthesized. These have been applied in conjunction with cobalt naphthenate in a facile, economic, and efficient method for the catalytic hydrosilylation of alkenes. In the presence of KOtBu as an additive, the reaction time and activation energy are greatly reduced.

Rare-Earth-Catalyzed Hydrosilylation and Dehydrogenative Coupling of Hydrosilanes

Activation of Si–H bonds with rare-earth complexes could generate the highly reactive rare-earth hydrides or silyl complexes, which are key intermediates for hydrosilylation and cross-coupling reactions. This Account summarizes the recent advances in the rare-earth-catalyzed hydrosilylation of unsaturated substrates and dehydrogenative coupling of hydrosilanes with amines in our laboratory. The results demonstrated that rare-earth catalysts are unique in their reactivity and selectivity, enabling some unprecedented reactions.1 Introduction2 Dehydrogenative Coupling of Hydrosilanes with Amines3 Catalytic Dehydrogenative Coupling of Hydrosilanes with Amines4 Catalytic Hydrosilylation of Terminal Alkenes and Polymerization of Styrene5 Catalytic Hydrosilylation of Internal Alkenes6 Catalytic Dihydrosilylation of Internal Alkynes7 Conclusions and Outlook