Rhodium‐Catalyzed Dynamic Kinetic Asymmetric Hydrosilylation to Access Silicon‐Stereogenic Center

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(51)

Опубликована: Ноя. 4, 2022

Abstract Strategies on the construction of enantiomerically pure silicon‐stereogenic silanes generally relies desymmetrization prochiral and symmetric substrates. However, dynamic kinetic asymmetric transformations organosilicon compounds have remained underdeveloped unforeseen owing to a lack an effective method for deracemization static silicon stereocenters. Here we report first Rh‐catalyzed intramolecular hydrosilylation (DyKAH) with “silicon‐centered” racemic hydrosilanes that enables facile preparation benzosiloles in good yields excellent enantioselectivities. The special rhodium catalyst controlled by non‐diastereopure‐type mixed phosphine‐phosphoramidite ligand axial chirality multiple stereocenters can induce enantioselectivity efficiently this novel DyKAH reaction. Density functional theory (DFT) calculations suggest amide moiety chiral plays important role facilitating S N 2 substitution chloride ion realize inversion center.

Язык: Английский

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Catalytic asymmetric silicon-carbon bond-forming transformations based on Si-H functionalization

Science China Chemistry, Год журнала: 2023, Номер 66(6), С. 1654 - 1687

Опубликована: Май 4, 2023

Язык: Английский

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Highly Enantioselective Construction of Multifunctional Silicon‐Stereogenic Silacycles by Asymmetric Enamine Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(9)

Опубликована: Янв. 10, 2023

We report the first highly enantioselective construction of silicon-stereocenters by asymmetric enamine catalysis. An unprecedented desymmetric intramolecular aldolization prochiral siladials was thus developed for facile access multifunctional silicon-stereogenic silacycles in high to excellent enantioselectivity. With an enal moiety, these adducts could be readily elaborated diverse synthesis compounds, and late-stage modification.

Язык: Английский

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Cobalt-Catalyzed Diastereo- and Enantioselective Carbon–Carbon Bond Forming Reactions of Cyclobutenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(6), С. 3588 - 3598

Опубликована: Фев. 3, 2023

Catalytic enantioselective functionalization of cyclobutenes constitutes a general and modular strategy for construction enantioenriched complex cyclobutanes bearing multiple stereogenic centers, as chiral four-membered rings are common motifs in biologically active molecules versatile intermediates organic synthesis. However, synthesis through such remained significantly limited. Herein, we report series unprecedented cobalt-catalyzed carbon-carbon bond forming reactions that initiated carbometalation. The protocols feature diastereo- introduction allyl, alkynyl, functionalized alkyl groups. Mechanistic studies indicated an unusual 1,3-cobalt migration subsequent β-carbon elimination cascade process occurred the allyl addition. These new discoveries established elementary cobalt catalysis extension diversity nucleophiles transformations cyclobutenes.

Язык: Английский

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

Chemical Society Reviews, Год журнала: 2024, Номер 53(17), С. 8546 - 8562

Опубликована: Янв. 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(48)

Опубликована: Авг. 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.

Язык: Английский

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

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 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

Язык: Английский

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Cobalt‐Catalyzed Regiodivergent and Enantioselective Intermolecular Coupling of 1,1‐Disubstituted Allenes and Aldehydes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(19)

Опубликована: Март 3, 2023

Catalytic enantioselective coupling of 1,1-disubstituted allenes and aldehydes through regiodivergent oxidative cyclization followed by stereoselective protonation or reductive elimination promoted chiral phosphine-Co complexes is presented. Such processes represent unprecedented unique reaction pathways for Co catalysis that enable catalytic generation metallacycles with divergent regioselectivity accurately controlled ligands, affording a wide range allylic alcohols homoallylic are otherwise difficult to access without the need pre-formation stoichiometric amounts alkenyl- allyl-metal reagents in up 92 % yield, >98 : 2 regioselectivity, dr >99.5 0.5 er.

Язык: Английский

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Photoredox cobalt-catalyzed regio-, diastereo- and enantioselective propargylation of aldehydes via propargyl radicals

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Авг. 10, 2023

Catalytic enantioselective introduction of a propargyl group constitutes one the most important carbon-carbon forming reactions, as it is versatile to be transformed into diverse functional groups and frequently used in synthesis natural products biologically active molecules. Stereoconvergent transformations racemic precursors single enantiomer via radicals represent powerful strategy provide new reactivity. However, only few Cu- or Ni-catalyzed protocols have been developed with limited reaction modes. Herein, photoredox/cobalt-catalyzed regio-, diastereo- addition aldehydes presented, enabling construction broad scope homopropargyl alcohols that are otherwise difficult access high efficiency stereoselectivity from carbonates. Mechanistic studies DFT calculations provided evidence for involvement radicals, origin stereoconvergent process stereochemical models.

Язык: Английский

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Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Авг. 19, 2023

We report a copper-catalyzed ligand-controlled selective 1,2- and 1,4-hydrosilylation of 1,3-enynes, which furnishes enantiomerically enriched propargyl- 1,2-allenylsilane products in high yields with excellent enantioselectivities (up to 99% ee). This reaction proceeds under mild conditions, shows broad substrate scope for both 1,3-enynes trihydrosilanes, displays regioselectivities. Mechanistic studies based on deuterium-labeling reactions density functional theory (DFT) calculations suggest that allenylcopper is the dominant reactive intermediate it undergoes metathesis silanes via four-membered or six-membered transition state, depending nature ligand. The weak interactions between ligands reacting partners are found be key controlling factor observed regioselectivity switch. origin enantiocontrol also revealed by level DLPNO-CCSD(T) calculations.

Язык: Английский

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