Catalytic asymmetric synthesis of silicon-stereogenic organosilanes

Chem, Год журнала: 2023, Номер 9(12), С. 3461 - 3514

Опубликована: Окт. 19, 2023

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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Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(7)

Опубликована: Янв. 5, 2024

Abstract A Cu‐catalyzed asymmetric synthesis of silicon‐stereogenic benzoxasiloles has been realized via intramolecular Si−O coupling [2‐(hydroxymethyl)phenyl]silanes. Cu(I)/difluorphos is found to be an efficient catalytic system for enantioselective Si−C bond cleavage and formation. In addition, kinetic resolution racemic substituted [2‐(hydroxymethyl)phenyl]silanes using Cu(I)/ PyrOx (pyridine‐oxazoline ligands) as the developed afford carbon‐ benzoxasiloles. Ring‐opening reactions chiral with organolithiums Grignard reagents yield various enantioenriched functionalized tetraorganosilanes.

Язык: Английский

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Lewis Base-Catalyzed Dynamic Kinetic Asymmetric Transformation of Racemic Chlorosilanes en Route to Si-Stereogenic Silylethers

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(33), С. 23092 - 23102

Опубликована: Авг. 7, 2024

Enantiopure Si-stereogenic organosilanes are highly valued in the fields of organic synthesis, development advanced materials, and drug discovery. However, they not naturally occurring, their synthesis has been largely confined to resolution racemic silanes or desymmetrization symmetric silanes. In contrast, dynamic kinetic asymmetric transformation (DYKAT) offers a mechanistically distinct approach would broaden accessibility an enantioconvergent manner. this study, we report Lewis base-catalyzed DYKAT chlorosilanes. The chiral isothiourea catalyst, (S)-benzotetramisole, facilitates silyletherification with phenols, yielding (R)-silylethers good yields high enantioselectivity (27 examples, up 86% yield, 98:2 er). Kinetic analysis, control experiments, DFT calculations suggest that two-catalyst-bound pentacoordinate silicate is responsible for Si-configurational epimerization ion-paired tetracoordinated silicon intermediates.

Язык: Английский

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Cu-Catalyzed Enantioselective Carbene Insertion into Ge–H and Si–H Bonds Enabled by SPSiBox with a Tunable Chiral Pocket

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 28, 2025

Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge-H and Si-H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed C2-symmetrical bisoxazoline ligands. This protocol provides an efficient method for preparation enantioenriched ogranogermanes organosilanes, featuring broad substrate scope, mild reaction conditions, excellent enantioselectivity, low catalyst loading. The key to tolerance is use SPSiBox ligands bearing flexible tunable chiral pocket. Preliminary mechanistic studies computational unveiled origin induction ligands, mechanism insertion. not only new construction trifluoromethyl-containing molecules but also opens avenue Si- Ge-containing functional molecules.

Язык: Английский

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Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июль 18, 2024

Abstract Despite impressive advances in the construction of enantioenriched silacarbocycles featuring silicon‐stereogenic centers via a selection well‐defined sila‐synthons, development more convenient and economic method with readily available starting materials is significantly less explored remains considerable challenge. Herein, we report first example copper‐catalyzed sequential hydrosilylation accessible methylenecyclopropanes (MCPs) primary silanes, affording an efficient route to wide range chiral silacyclopentanes bearing consecutive silicon‐ carbon‐stereogenic excellent enantio‐ diastereoselectivities (generally ≥98 % ee, >25 : 1 dr). Mechanistic studies reveal that these reactions combine intermolecular ring‐opening aryl MCPs intramolecular asymmetric resultant Z / E mixture homoallylic silanes.

Язык: Английский

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Divergent Synthesis of Enantioenriched Silicon‐Stereogenic Benzyl−, Vinyl− and Borylsilanes via Asymmetric Aryl to Alkyl 1,5‐Palladium Migration

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июль 30, 2024

Functionalization of Si-bound methyl group provides an efficient access to diverse organosilanes. However, the asymmetric construction silicon-stereogenic architectures by functionalization has not yet been described despite recent significant progress in producing chiral silicon. Herein, we disclosed enantioselective silylmethyl involving aryl alkyl 1,5-palladium migration naphthalenes possessing enantioenriched stereogenic silicon center, which are inaccessible before. It is worthy note that realization induction at step metal itself remains challenging. Our study constitutes first reaction. The key success discovery and fine-tuning different substituents α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based phosphoramidites, ensure enantioselectivity desired reactivity.

Язык: Английский

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Rh-Catalyzed Enantioselective Desymmetric Hydrogenation of α-Acetamido-1,3-indanediones Using Ether-Bridged Biphenyl Diphosphine Ligands

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(39), С. 21176 - 21182

Опубликована: Авг. 23, 2023

Novel axially chiral biphenyl diphosphine ligands Enm-BridgePhos, bearing an ether chain bridge at the 5,5'-position of backbone, have been developed and successfully applied in Rh-catalyzed enantioselective desymmetric hydrogenation α-acetamido-1,3-indanediones, providing α-acetamido-β-hydroxybenzocyclic pentones high yields (up to 97%) with excellent enantioselectivities 99% ee). The reaction could be carried out on a gram scale, corresponding products were used as vital intermediates for synthesis analogues spirobenzylisoquinoline alkaloids. Both crystal structure analysis DFT calculations revealed that large dihedral angle Enm-BridgePhos-Rh complexes is highly related enantioselectivities.

Язык: Английский

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Development of a One-Step Synthesis of oxa-Spirocyclic Diphosphine Ligands Driven by Their Application in the Industrial Synthesis of Sacubitril

Organic Letters, Год журнала: 2024, Номер 26(14), С. 2811 - 2816

Опубликована: Янв. 16, 2024

Herein we have developed a highly practical and efficient one-step coupling protocol for the synthesis of chiral spiro diphosphine ligands, especially oxa-spiro ligands O-SDP, which showed excellent reactivity diastereoselectivity in asymmetric hydrogenation key intermediate Sacubitril. It should be noted that could operated on kilogram scale, resulting ruthenium catalyst O-SDP hydrogenate Sacubitril an industrial scale.

Язык: Английский

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Design and Synthesis of Chiral Spiro Monophosphinites with a 3-Oxo-1,1′-spirobiindane Scaffold and Their Application in Rhodium-Catalyzed Asymmetric Hydrogenation of Dehydroamino Acid Esters

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 15, 2025

A new class of chiral spiro monophosphinites, based on a unique non-C2-symmetric 3-oxo-1,1'-spirobiindane scaffold featuring large dihedral angle, has been effectively designed and synthesized. From readily accessible resources, these monophosphinites were synthesized via eight steps in 16-32% yields. Their excellent performance the rhodium-catalyzed asymmetric hydrogenation β-dehydroamino acid esters underscores critical impact angle enhancing activity enantioselectivity.

Язык: Английский

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