Enantioselective Synthesis of Axially Chiral Silacyclohexylidene Oxime Ethers by Chiral Phosphoric Acid Catalysis DOI
Xiyu Wang, Xingang Xie, Zhongwei Wu

et al.

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Abstract The first asymmetric condensation of prochiral silacyclohexanones with hydroxylamines by chiral phosphoric acid catalysis has been developed, which provides a facile and straightforward protocol for the enantioselective construction valuable axially silacyclohexylidene oxime ethers that are otherwise inaccessible. Notably, this constitutes rare example accessing silacycles featuring axial chirality.

Language: Английский

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

Sheng-Ye Zhang,

Ziyang Chen

et al.

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

Citations

0
Recent Progress in the Synthesis of Silaspiranes DOI Open Access
Hua Chen, Xuejiao Hu,

Wanshu Wang

et al.

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

Citations

7
Rhodium-Catalyzed Asymmetric Hydroboration/Cyclization of 1,6-Enynes Enabled by Spirosiladiphosphine Ligands: Constructing Chiral Five-Membered Rings with a Boron Handle DOI
Fei Hou, Yingtang Ning, Lili Song

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(43), P. 7810 - 7815

Published: Oct. 26, 2023

A rhodium-catalyzed enantioselective hydroboration/cyclization reaction of 1,6-enynes is achieved by employing a spirosiladiphosphine ligand. The process allows the synthesis five-membered hetero- and carbocycles bearing boron handle with high levels activity selectivity. Various enynes organoboranes (HBdan, HBpin, HBmp, HBamm) have been accommodated, containing terminal alkynes integrated into for first time. yields selectivities transformation highlight synthetic utility these novel ligands.

Language: Английский

Citations

7
Application of hydrazone ligands in Chan−Lam coupling of arylboronic acids and thiols DOI

Legen Hu,

Jiaquan Wang,

Kelun Cui

et al.

Tetrahedron, Journal Year: 2024, Volume and Issue: 156, P. 133945 - 133945

Published: March 14, 2024

Language: Английский

Citations

2
Intramolecular Hosomi–Sakurai Reaction for the Synthesis of Benzoxasiloles DOI

Xin‐Long Yu,

Jiawei Hu, Jian Cao

et al.

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

Citations

1
Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes DOI
Bin Fu, Lianghua Wang, Kexin Chen

et al.

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

Citations

1
Carbon-silicon-switch effect in enantioselective construction of silicon-stereogenic center from silacyclohexadienones DOI Creative Commons
Yu Yan, Qi Wei, Zhishan Su

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 15, 2024

Carbon-silicon-switch strategy, replacing one specific carbon atom in organic molecules with a silicon, has garnered significant interest for developing new functional molecules. However, the influence of reaction regarding its selectivity and reactivity by carbon-silicon-switch strategy far less been investigated. Here we discover an unusual effect enantioselective construction silicon-stereogenic center. It is found that there change desymmetrization silacyclohexadienones using asymmetric conjugate addition or oxidative Heck aryl/alkyl nucleophiles when compared their analogues cyclohexadienones. Specifically, leads to reversal enantioselectivity arylzinc as nucleophile same chiral catalyst, results totally different arylboronic acid nucleophile. Control experiments density theory (DFT) calculations have shown comes from unique stereoelectronic feature silicon. Silicon incorporated into place under principle that, given they belong periodic group, could be similar. Here, authors perform desymmetrizations on silacyclohexenone analogue, two substrates yielding opposite enantiomers, showing our understanding similarities atoms incomplete.

Language: Английский

Citations

1
Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles DOI

Wan‐Er Gan,

Yong‐Shun Wu,

Bin Wu

et al.

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

Citations

1
Development and Application of SPOSiPs: A Class of Diphosphine Ligands Based on SPOSiOL DOI
Zedong Li, Fei Ren, Yichen Wu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7436 - 7441

Published: Aug. 26, 2024

Here, we report the development and application of a novel class spirosilacycle-based diphosphine ligands (SPOSiPs). This type ligand could be readily prepared in two steps with high efficiency starting from enantiopure spirobiphenoxasilin-diol (SPOSiOL). According to structural analysis SPOSiP its PdCl2 complex, SPOSiPs possess flexible chiral pocket feature rigid configuration, large dihedral angle, long P–P distance, P–M–P bite angle their metal complexes. The potentials asymmetric catalysis have also been preliminarily disclosed.

Language: Английский

Citations

1
Divergent Synthesis of Enantioenriched Silicon‐Stereogenic Benzyl‐, Vinyl‐ and Borylsilanes via Asymmetric Aryl to Alkyl 1,5‐Palladium Migration DOI
Yufeng Shi, Ying Qin,

Zhong‐Qiu Li

et al.

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

Citations

0