SPSiPs, a Class of Diphosphine Ligands Based on SPSiOL with a Large Dihedral Angle

Organic Letters, Journal Year: 2023, Volume and Issue: 25(21), P. 3859 - 3863

Published: May 22, 2023

The development and the synthetic applications of a novel class diphosphine ligands (SPSiPs) based on chiral spirosilabiindane diol (SPSiOL) are presented. Starting from SPSiOL, could be readily prepared in three steps with high efficiency. This features rigid configuration, large dihedral angle, P-M-P long P-P distance. potentials SPSiPs asymmetric catalysis have also been preliminarily disclosed.

Language: Английский

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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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Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(7)

Published: Jan. 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.

Language: Английский

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Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 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.

Language: Английский

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Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(13), P. 6735 - 6778

Published: Jan. 1, 2024

The review summarizes the increasing applications of chiral bisphosphine ligand Ph-BPE in catalytic asymmetric reactions past twenty years.

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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Selective Hydrosilylation and Hydroboration of Allenes Catalyzed by Cobalt‐Pincer Complexes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(12), P. 2775 - 2783

Published: April 24, 2024

Abstract Achieving precise control over regioselectivity and stereoselectivity in the hydroelementation of terminal allenes presents a formidable challenge. Despite existence various catalytic methods for their functionalization, this entire class reactions remains significantly underdeveloped demands extensive research. Here, we report method using inexpensive PN 5 P pincer cobalt complexes built on triazine backbone. Depending substituent at ring, enables selective synthesis E‐alkenylsilane or Z‐allylborane derivatives. In presented approach, silanes pinacoloboranes play dualistic role simultaneous activator substrate excluding need addition external bases. Finally, application potential obtained compounds was demonstrated by performing further functionalizations compounds.

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: April 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.

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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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, Journal Year: 2025, Volume and Issue: unknown

Published: April 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.

Language: Английский

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