Organocatalytic enantioselective construction of Si-stereocenters: recent advances and perspectives

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(17), P. 8546 - 8562

Published: Jan. 1, 2024

Silicon-stereogenic chiral organosilanes have found increasing applications in synthetic chemistry, medicinal and materials science. In this context, various asymmetric catalytic methods been established for the diverse synthesis of silicon-stereogenic silanes. particular, organocatalysis is emerging as an important complementary tool enantioselective construction silicon-stereocenters, along with rapid development chiral-metal catalyzed protocols. Its advent provides a powerful platform to achieve functionalized structural diversity, should lead great organosilicon chemistry. Tutorial Review, we highlight these latest achievements from two aspects: desymmetrizations prochiral tetraorganosilanes dynamic kinetic transformations racemic by employing five organocatalytic activation modes. The advantages, limitations value each protocol, well opportunities still open further exploration, are also discussed.

Language: Английский

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Catalytic Asymmetric Construction of C‐ and Si‐Stereogenic Silacyclopentanes via Hydrosilylation of Arylmethylenecyclopropanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 14, 2024

Silacycles have exhibited significant potential for application in the fields of medicinal chemistry, agrochemistry, and materials science. Accordingly, development effective methods synthesizing these compounds has attracted increasing attention. Here, we report an efficient Cu-catalyzed enantioselective hydrosilylation arylmethylenecyclopropanes with hydrosilanes, that allows rapid assembly various enantioenriched carbon- silicon-stereogenic silacyclopentanes good yields excellent enantioselectivities diastereoselectivities under mild conditions. Further stereospecific transformation Si-H bond on chiral silicon center expands diversity C- Si-stereogenic silacyclopentanes.

Language: Английский

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Copper-catalyzed intermolecular Regio- and Enantioselective Hydrosilylation of Alkenes with Prochiral Silanes

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 3, 2025

This study presents a copper-catalyzed, substrate-controlled regio- and enantioselective intermolecular hydrosilylation method capable of accommodating broad scope alkenes prochiral silanes. The approach offers an efficient versatile pathway to generate enantioenriched linear branched alkyl-substituted Si-stereogenic Key features this reaction include mild conditions, simple catalytic systems, compatibility with diverse substrates, high yields enantioselectivities. While methods create chiral carbon centers stereochemically defined silicon have been developed, the ability both simultaneously would be value. Here authors present substratecontrolled

Language: Английский

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Construction of axial and point chirality through Ni-catalyzed sila-cycloaddition reaction via desymmetrization and (dynamic) kinetic resolution

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Language: Английский

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Cobalt-Catalyzed Regioselective Intramolecular Hydrosilylation of Olefins to Access Sila-heterocycles

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

An efficient and straightforward cobalt-catalyzed regioselective intramolecular hydrosilylation of olefins has been developed. Regioselectivity is controlled by the choice ligands substrates, which operate through two distinct mechanisms. This method successfully applied to both terminal internal alkenes phenyl alkyl tethers between silane alkene, demonstrating its versatility across a broad range substrates.

Language: Английский

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Catalytic Reductive (Double) [4+1] Sila-cycloaddition of 1,3-Dienes with Di-, Tri-, and Tetrachlorosilane(s) Enabled by the Pyridine–Diimine–Nickel Complex

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Herein, we report a catalytic reductive [4+1] sila-cycloaddition between functionalized 1,3-dienes and chemical feedstock di-, tri-, tetrachlorosilane(s), enabled by cost-effective pyridine-diimine-nickel complex, providing practical method to prepare diverse silacyclopent-3-enes in up 92% yield, including bridged spiro silacarbocycles. This reaction demonstrates broad substrate compatibility, with different substitution patterns more accessible E/Z isomeric mixture. Notably, trichlorosilanes undergo tandem sila-cycloadditions/nucleophilic substitutions, while tetrachlorosilane successfully performs double sila-cycloadditions 2 equiv of directly construct

Language: Английский

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Kinetic Resolution of Amino Acids by Phosphine Oxide Catalyzed Enantioselective Esterification

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: May 7, 2025

The first highly efficient kinetic resolution (KR) of racemic amino acids with L-pyroglutaminol as an esterification reagent was reported through a novel phosphine oxide organocatalyst catalyzed under mild conditions, which provides wide range chiral esters and recovered excellent stereoselectivities (s > 1057). catalyst demonstrated stereocontrol catalytic activity, presumably benefited from intimate double H-bonding interaction between the pyroglutaminol core catalyst. Chiral find applications versatile building blocks in synthesis functional molecules, source information asymmetric tools to expand explore function native biological machinery.^1–8 Therefore, represent class valuable indispensable compounds whose stereoselective is major objective within synthetic chemists biologists.^9–10 To best our knowledge, array effective strategies for construction have been developed, such hydrogenation nucleophilic addition imines^11–18, enantioselective carbene insertion into N-H bonds amines or amides^19–23, photobiocatalytic cross-coupling^24–27, stereocontrolled 1,3-nitrogen migration carboxylic acids²⁸. However, identifying specific reaction not always easy task. An alternative well-established strategy relies on KR mixture (Fig. 1a).^29–31 stands out one most practical straightforward obtaining enantioenriched molecules recovering starting materials, effectively allowing access both enantiomers single enantiomer Numerous processes developed that reliably deliver enantiopure compounds, including alcohols^32–36, monohydrosilanes³⁷, organoperoxides³⁸, alkynes^39–40, sulfonyl ketones⁴¹, amines⁴², imines⁴³, sulfoximines^44–45, aldehydes⁴⁶, phosphindane oxides^47–48, heterocyclic compounds^49–52. Despite this significant progress field, remains challenging task has rarely explored.^53–57

Language: Английский

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Iron-catalyzed sequential hydrosilylation

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: May 9, 2025

Highly regio-, diastereo- and enantioselective iron-catalyzed sequential hydrosilylation of o-alk-n-enyl-phenyl silanes with alkynes is reported for various 5-, 6-, 7-membered benzosilacycles in 60-94% yields up to 95:5 rr, dr, 99% ee. Chiral fully carbon-substituted silicon-stereogenic could also be obtained via triple reactions. The unique electronic effect ligands observed while adjusting the regioselectivity enantioselectivity A possible mechanism has been proposed by variable time normalization analysis (VTNA) H/D exchange experiment.

Language: Английский

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Catalytic Asymmetric Construction of C‐ and Si‐Stereogenic Silacyclopentanes via Hydrosilylation of Arylmethylenecyclopropanes

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(48)

Published: Aug. 14, 2024

Abstract Silacycles have exhibited significant potential for application in the fields of medicinal chemistry, agrochemistry, and materials science. Accordingly, development effective methods synthesizing these compounds has attracted increasing attention. Here, we report an efficient Cu‐catalyzed enantioselective hydrosilylation arylmethylenecyclopropanes with hydrosilanes, that allows rapid assembly various enantioenriched carbon‐ silicon‐stereogenic silacyclopentanes good yields excellent enantioselectivities diastereoselectivities under mild conditions. Further stereospecific transformation Si−H bond on chiral silicon center expands diversity C‐ Si‐stereogenic silacyclopentanes.

Language: Английский

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Efficient and stable NiMo alloy nanoparticles on ZSM-5 for alkene hydrosilylation

Journal of Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 1019, P. 123279 - 123279

Published: July 22, 2024

Language: Английский

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