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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: July 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.

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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Novel Sulfinamide-Based Chiral Ligand Promoted Chiral Diarylmethanol Preparation via exo-Directed Asymmetric C–H Alkynylation under Mild Conditions

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2540 - 2549

Published: Jan. 28, 2025

Language: Английский

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Palladium-catalyzed double activation of Si-C(sp3) bond of benzosilacyclobutenes synergized with unexpected olefin migration and ring-opening hydrolysis

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 440, P. 115788 - 115788

Published: Oct. 10, 2024

Language: Английский

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Synthesis of Si-Stereogenic Silanols via Pd-Catalyzed C–H Alkenylation

Synfacts, Journal Year: 2024, Volume and Issue: 20(06), P. 0602 - 0602

Published: May 14, 2024

Key words palladium catalysis - C–H functionalization alkenylation

Language: 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, Journal Year: 2024, Volume and Issue: 136(36)

Published: June 19, 2024

Abstract 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.

Language: Английский

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Nickel-catalyzed stereospecific reductive cross-coupling of vinyl chlorosilanes with axially chiral biaryl electrophiles

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(96), P. 14204 - 14207

Published: Jan. 1, 2024

Nickel-catalyzed stereospecific reductive cross-coupling of vinyl chlorosilanes with chiral biaryl electrophiles for the synthesis axially organosilanes.

Language: Английский

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