Synthesis of Some New Chiral Triazole-oxazoline Derivatives DOI
Hong‐Ru Dong

Current Organic Synthesis, Journal Year: 2024, Volume and Issue: 22(1), P. 136 - 142

Published: July 12, 2024

: Some new (S)-2-[1-aryl-5-methyl-1H-1,2,3-triazol-4-yl]-4-benzyl-4,5-dihydro-ox-azoline were synthesized by the reaction of (S)-N-(1-hydroxy-3-phenylpropan-2-yl)-1-aryl-5-methyl-1H-1,2,3-triazole-4-carboxamides which prepared from aromatic amine as start-ing materials, with p-toluenesulfonyl chloride, triethylamine and DMAP. The structures characterized 1H NMR, 13C MS IR. chiral triazole-oxazoline was used a ligand in Diels-Alder asymmetric catalytic between 3-allyl-1,3-ox-azolidin-2-ketone 2-methyl-1,3-butadiene, using PdCl2 catalyst. (S)-3-(4-methylcyclo-hexe-3-ene-1-formyl)-1,3-oxazolidin-2-one obtained. Background: ligands are rarely reported. Objective: aim study to synthsize some (S)-4-benzyl-2-(1-aryl-5-methyl-1H-1,2,3-triazole-4-yl)-4,5-dihydrooxazoline (5a-g). Methods: one-pot methods oriented synthesis adopted. This provides sim-ple effective method for derivatives. Results: (5a-g) cyclization 3-allyl-1,3-oxazolidin-2-ketone 2-methyl-1,3-butadiene catalyzed (S)-4-triazole-oxazoline ligands. Conclusion: (S)-4-benzyl-2-(1-aryl-5-methyl-1H-1,2,3-triazole-4-yl)-4,5-dihydro-oxazoline corresponding N-[(S)-1-hydroxy-3-phenylpropan-2-yl]-1-aryl-5-methyl-1H-1,2,3-triazole-4-formamide, through method. After preliminary evaluation, triazoline-oxazoline ligands, 1,2,3-triazole rings, like pyridine-type materials saved replace one oxazoline ring di-oxazoline reactions.

Language: Английский

Organocatalytic enantioselective construction of Si-stereocenters: recent advances and perspectives DOI

Zhong-Tian Ye,

Zhongwei Wu,

Xue‐Xin Zhang

et al.

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

Citations

13
Catalytic Asymmetric Construction of C‐ and Si‐Stereogenic Silacyclopentanes via Hydrosilylation of Arylmethylenecyclopropanes DOI

Liexin Wu,

Lu Zhang, Jiandong Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 14, 2024

Silacycles have exhibited significant potential for application in the fields of medicinal chemistry, agrochemistry, and materials science. Accordingly, development effective methods synthesizing these compounds has attracted increasing attention. Here, we report an efficient Cu-catalyzed enantioselective hydrosilylation arylmethylenecyclopropanes with hydrosilanes, that allows rapid assembly various enantioenriched carbon- silicon-stereogenic silacyclopentanes good yields excellent enantioselectivities diastereoselectivities under mild conditions. Further stereospecific transformation Si-H bond on chiral silicon center expands diversity C- Si-stereogenic silacyclopentanes.

Language: Английский

Citations

12
Copper-catalyzed intermolecular Regio- and Enantioselective Hydrosilylation of Alkenes with Prochiral Silanes DOI Creative Commons
Xiaoyan Zhu,

Wenyu Gao,

Jian‐Lin Xu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 3, 2025

This study presents a copper-catalyzed, substrate-controlled regio- and enantioselective intermolecular hydrosilylation method capable of accommodating broad scope alkenes prochiral silanes. The approach offers an efficient versatile pathway to generate enantioenriched linear branched alkyl-substituted Si-stereogenic Key features this reaction include mild conditions, simple catalytic systems, compatibility with diverse substrates, high yields enantioselectivities. While methods create chiral carbon centers stereochemically defined silicon have been developed, the ability both simultaneously would be value. Here authors present substratecontrolled

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 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

Citations

5
Construction of axial and point chirality through Ni-catalyzed sila-cycloaddition reaction via desymmetrization and (dynamic) kinetic resolution DOI
Hua‐Jie Zhu, Minghao Shen,

Jia-Wei Si

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Language: Английский

Citations

0
Highly selective monosubstitution of symmetrical dialkoxysilanes in continuous flow: Kinetics and mechanisms research DOI
Jiadi Zhou, Shoumin Bai, Weilong Zhang

et al.

The Canadian Journal of Chemical Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Abstract Monosubstituted symmetrical dialkoxysilanes, intermediates in the production of numerous well‐known materials, present challenges for selective monosubstitution due to presence two alkoxy groups similar chemical environments. Notably, kinetic studies on this phenomenon have not been documented. In addressing knowledge gap, we developed a continuous flow system reaction kinetics between diethoxydimethylsilane and vinyl magnesium chloride, enhancing our understanding these reactions. We initially analyzed order, pre ‐exponential factors, activation energies systematically. The investigation revealed that partial order was first‐order, chloride also overall second‐order. energy main 39.21 kJ/mol, side 59.72 kJ/mol. Therefore, precise control conditions is essential improving yield. This identified potential mechanism, which later confirmed through series experiments. These experiments accurately determined applicable concentration temperature ranges model. Further, simulations model assessed influences molar ratios selectivity, aiming achieve controlled outcomes. study provides new insights into Grignard reagents with dialkoxysilanes offers valuable guidance optimizing industrial applications. demonstrates laminar reactor. Compared traditional batch processes, reactor achieved milder higher reaching 99.5% selectivity 97.9% yield simulations.

Language: Английский

Citations

0
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

2
Advances in disilylation reactions to access cis/trans-1,2-disilylated and gem-disilylated alkenes DOI

Shasha Geng,

Yu Pu, Siyu Wang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(26), P. 3484 - 3506

Published: Jan. 1, 2024

Organosilane compounds are widely used in both organic synthesis and materials science.

Language: Английский

Citations

1
Catalytic Asymmetric Construction of C‐ and Si‐Stereogenic Silacyclopentanes via Hydrosilylation of Arylmethylenecyclopropanes DOI

Liexin Wu,

Lu Zhang, Jiandong Guo

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(48)

Published: Aug. 14, 2024

Abstract Silacycles have exhibited significant potential for application in the fields of medicinal chemistry, agrochemistry, and materials science. Accordingly, development effective methods synthesizing these compounds has attracted increasing attention. Here, we report an efficient Cu‐catalyzed enantioselective hydrosilylation arylmethylenecyclopropanes with hydrosilanes, that allows rapid assembly various enantioenriched carbon‐ silicon‐stereogenic silacyclopentanes good yields excellent enantioselectivities diastereoselectivities under mild conditions. Further stereospecific transformation Si−H bond on chiral silicon center expands diversity C‐ Si‐stereogenic silacyclopentanes.

Language: Английский

Citations

1
Chemodivergent, enantio- and regioselective couplings of alkynes, aldehydes and silanes enabled by nickel/N-heterocyclic carbene catalysis DOI
Jiaming Liu, Xuexiang Ma, Guang Chen

et al.

Science Bulletin, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 1, 2024

Language: Английский

Citations

1