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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Nickel-Catalyzed Mono- and Dihydrosilylation of Aliphatic Alkynes in Aqueous and Aerobic Conditions

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5077 - 5087

Published: March 20, 2024

1,1-Disilanes are synthetically versatile building blocks, owing to their low toxicity, high stability, and unique structures. However, the practical synthesis of 1,1-disilanes is still a challenge. Despite available Fe-, Co-, La-, B-catalyzed protocols, use highly reactive reductants, such as EtMgBr, NaBHEt3, or KHMDS, inevitably requires air- moisture-free conditions. Herein, we report homogeneous Ni-catalyzed mono- dihydrosilylation aliphatic terminal alkynes under either air water conditions neat conditions, affording β-(E)-vinylsilanes in yields with complete regioselectivity stereoselectivity. Importantly, our method gram-scalable sole example alkynes. We demonstrated introduction different silyl groups through stepwise addition each silane source reaction vessel. Furthermore, intermediates were characterized spectroscopic/spectrometric tools, density functional theory calculations performed understand mechanism origins for 1,1-disilanes.

Language: Английский

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Update Hydrometallation Group 4 (Si, Ge and Sn)

Elsevier eBooks, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Language: Английский

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Recent Progress in the Synthesis of Silaspiranes

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(70)

Published: Sept. 23, 2023

Abstract Silaspiranes bearing a spiro‐silicon center are promising ring frameworks for the synthesis of novel spirocyclic molecules possessing unique properties. Development efficient methods towards these structures has therefore attracted considerable attentions synthetic chemists. This minireview highlights representative advances in field, and is categorized into four parts according to formation strategies: cyclization, annulation, expansion cycloaddition.

Language: Английский

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Nickel-Catalyzed Regio- and Stereoselective Hydroalkylation of Allenes: Exploiting the Unique Reactivity of Diazo Compounds as an Alkylating Source

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(22), P. 16570 - 16576

Published: Oct. 25, 2024

The reactivity of allenes has historically been limited with no previous examples their hydroalkylation using diazo compounds in any transition-metal catalytic framework. In this study, we present a Ni-catalyzed regio- and stereoselective reaction utilizing as alkylating agents. success method can be attributed to the use pyridine-based P,N ligand, which combines advantages both phosphine nitrogen ligands. Additionally, carbonyl group compound facilitates formation stable intermediates. Our detailed mechanistic studies reveal that proceeds through an initial interaction compound, followed by engagement allene.

Language: Английский

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Decarboxylative Allylation of Silanecarboxylic Acids Enabled by Organophotocatalysis

Organic Letters, Journal Year: 2023, Volume and Issue: 25(40), P. 7406 - 7411

Published: Oct. 2, 2023

Herein we present a visible-light-facilitated transition-metal-free allylic silylation reaction under mild conditions. This protocol is enabled by an inexpensive organophotocatalyst and provides efficient concise synthetic routes to substituted allylsilanes, particularly from readily available allyl sulfones stable silanecarboxylic acids as silyl radical precursors. Further investigations reveal that this strategy also generally compatible with vinyl access vinylsilanes. The silver catalytic system opens up alternative entry realize the decarboxylative allylation of acids.

Language: Английский

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Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Journal Year: 2023, Volume and Issue: 27(11), P. 1913 - 1930

Published: Sept. 13, 2023

As the field of nonprecious metal catalysis continues to expand, we pursue a review series covering selected transformations in this area over short time interval highlight advancements. We seek raise awareness both current art and need continue development toward broader application or earth-abundant metals chemical pharmaceutical industries.

Language: Английский

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Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(7)

Published: Jan. 8, 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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Intramolecular Hosomi–Sakurai Reaction for the Synthesis of Benzoxasiloles

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 9027 - 9030

Published: May 30, 2024

A Lewis acid-catalyzed intramolecular Hosomi–Sakurai reaction of o-(allylsilyl)benzaldehyde/ketone has been developed. The proceeds through simultaneous C–Si bond cleavage and C–C reconstruction. This protocol provides a rapid approach for the synthesis allyl-substituted benzoxasiloles under mild conditions.

Language: Английский

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Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(42)

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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