When complexed by selected ligands in either the BIPHEP or the SEGPHOS series, CuH is an extremely reactive catalyst capable of effecting asymmetric hydrosilylations of aromatic ketones at temperatures between -50 and -78 degrees C. Inexpensive silanes serve as stoichiometric sources of hydride. Substrate-to-ligand ratios exceeding 100000:1 have been documented. The level of induction is usually in the >90% ee category. The nature of the reagent has been investigated using spectroscopic and chemical means, although its composition remains unclear.

Download full-text PDF

Source
http://dx.doi.org/10.1021/ja021391fDOI Listing

Publication Analysis

Top Keywords

asymmetric hydrosilylation
4
hydrosilylation aryl
4
aryl ketones
4
ketones catalyzed
4
catalyzed copper
4
copper hydride
4
hydride complexed
4
complexed nonracemic
4
nonracemic biphenyl
4
biphenyl bis-phosphine
4

Similar Publications

Catalytic Asymmetric Dehydrogenative Si-H/X-H Coupling toward Si-Stereogenic Silanes.

Acc Chem Res

January 2025

Shenzhen Grubbs Institute and Department of Chemistry, Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.

ConspectusChiral organosilicon compounds bearing a Si-stereogenic center have attracted increasing attention in various scientific communities and appear to be a topic of high current relevance in modern organic chemistry, given their versatile utility as chiral building blocks, chiral reagents, chiral auxiliaries, and chiral catalysts. Historically, access to these non-natural Si-stereogenic silanes mainly relies on resolution, whereas their asymmetric synthetic methods dramatically lagged compared to their carbon counterparts. Over the past two decades, transition-metal-catalyzed desymmetrization of prochiral organosilanes has emerged as an effective tool for the synthesis of enantioenriched Si-stereogenic silanes.

View Article and Find Full Text PDF

Rhodium-Catalyzed Enantioselective Hydrosilylation of 1,1-Disubstituted Enamides.

Org Lett

December 2024

Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121, P. R. China.

Catalytic hydrosilylation of 1,1-disubstituted enamides is one of the most challenging and synthetically useful processes in organosilicon chemistry and asymmetric catalysis. Herein, we report a rhodium-catalyzed enantioselective hydrosilylation of α-arylenamides with substituted hydrosilanes with the aid of chiral P-ligand, including newly developed spirophosphite ligands, giving various chiral β-silylated amides in excellent yields with good to excellent enantioselectivities (98:2 er after recrystallization). In addition, chiral β-silylated amines can be obtained by further functionalization of the hydrosilylation product.

View Article and Find Full Text PDF

An operationally convenient cobalt-catalyzed one-pot one-step hydrosilylation/hydroboration reaction of arylidenecyclopropanes is developed to access racemic 1,4-borylsilylalkanes. In addition, the corresponding asymmetric reaction is developed with a chiral copper catalyst to prepare 1,4-borylsilylalkanes with high enantioselectivity by a one-pot two-step procedure. Mechanistic studies reveal that this difunctionalization process begins with metal-hydride-catalyzed ring-opening hydrosilylation of arylidenecyclopropanes to generate homoallylsilane intermediates, followed by regio- or enantioselective metal-hydride-catalyzed hydroboration of homoallylsilanes to produce skipped borylsilylalkanes.

View Article and Find Full Text PDF

Rhodium-catalyzed synthesis of Si-stereogenic alkoxysilanes and silyl enol ethers hydrosilylation of carbonyl compounds.

Chem Commun (Camb)

November 2024

Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.

A highly efficient rhodium-catalyzed asymmetric hydrosilylation of aldehydes, ketones, and α,β-unsaturated ketones with dihydrosilanes is developed, that allows the rapid assembly of a variety of Si-stereogenic alkoxysilanes and silyl enol ethers in good yields and enantioselectivities under mild conditions. The applicability of this methodology was demonstrated by a series of stereospecific transformations to construct diverse Si-stereogenic derivatives.

View Article and Find Full Text PDF

Advances in Chiral Pincer Complexes: Insights and Applications in Catalytic Asymmetric Reactions.

Int J Mol Sci

September 2024

Natural Compounds and Organic Synthesis Laboratory, Migal-Galilee Research Institute, Kiryat Shmona 11016, Israel.

Chiral pincer complexes, characterized by their rigid tridentate coordination framework, have emerged as powerful catalysts in asymmetric synthesis. This review provides a comprehensive overview of recent advancements in the development of chiral pincer-type ligands and their corresponding transition metal complexes. We highlight the latest progress in their application across a range of catalytic asymmetric reactions, including the (transfer) hydrogenation of polar and non-polar bonds, hydrophosphination, alkynylation, Friedel-Crafts reactions, enantioselective reductive cyclization of alkynyl-tethered cyclohexadienones, enantioselective hydrosilylation, as well as Aza-Morita-Baylis-Hillman reactions.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!