Copper-Catalyzed Enantioselective Desymmetric Protosilylation of Prochiral Diynes: Access to Optically Functionalized Tertiary Alcohols DOI
Zhiyuan Chen,

Meng‐Wei Yang,

Zi‐Lu Wang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(28), P. 5242 - 5247

Published: July 7, 2023

In this protocol, a copper-catalyzed desymmetric protosilylation of prochiral diynes was developed. The corresponding products were obtained in moderate to high yields and enantiomeric ratios. This approach provides simple method for synthesizing functionalized chiral tertiary alcohols the presence pyridine-bisimidazoline (Pybim) ligand.

Language: Английский

Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes DOI
Hua Chen,

Ju Peng,

Qinjiao Pang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(48)

Published: Oct. 7, 2022

Silaspiranes have attracted particular attention due to their chiral spiro-silicon center, which serves as an ideal carbon isostere and can endow spiro-analogs with distinct properties. Distinct from previously reported cyclization or cycloaddition strategies form 5/5-silaspiranes, we report herein the asymmetric dual ring expansion of spirosilabicyclobutanes alkynes synthesize axially spirosilabicyclohexenes bearing a novel 6/6-silaspirane framework. DFT (density functional theory) calculations provide deep insight into origin high enantioselectivity controlled by sterically demanding binaphthyl phosphoramidite ligand. Preliminary studies chiroptical properties indicate that one spirosilabicyclohexene analogs exhibit fluorescence emission, Cotton effects CPL (circularly polarized luminescence) activity.

Language: Английский

Citations

50
Synthetic strategies to access silacycles DOI Creative Commons
Fengjuan Chen, Luo Liu, Wei Zeng

et al.

Frontiers in Chemistry, Journal Year: 2023, Volume and Issue: 11

Published: June 15, 2023

In comparison with all-carbon parent compounds, the incorporation of Si-element into carboskeletons generally endows corresponding sila-analogues unique biological activity and physical-chemical properties. Silacycles have recently shown promising application potential in chemistry, pharmaceuticals industry, material chemistry. Therefore, development efficient methodology to assemble versatile silacycles has aroused increasing concerns past decades. this review, recent advances synthesis silacycle-system are briefly summarized, including transition metal-catalytic photocatalytic strategies by employing arylsilanes, alkylsilane, vinylsilane, hydrosilanes, alkynylsilanes, etc. as starting materials. Moreover, a clear presentation understanding mechanistic aspects features these developed reaction methodologies been high-lighted.

Language: Английский

Citations

19
Ligand-Controlled Regiodivergent Ring Expansion of Benzosilacyclobutenes with Alkynes en Route to Axially Chiral Silacyclohexenyl Arenes DOI

Xiaoxiao Tang,

Yulang Tang,

Ju Peng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 21, 2024

A ligand-controlled regiodivergent and enantioselective ring expansion of benzosilacyclobutenes with internal naphthyl alkynes has been achieved by adjusting the ligand cavity size. The (

Language: Английский

Citations

7
Synthesis of Difluorocyclopropanes via a Photoinduced [1＋2] Cycloaddition of Diazo Esters with gem-Difluoroalkenes DOI

Xiaonan Mu,

Mingyu Guan, Yongsheng Niu

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(1), P. 256 - 256

Published: Jan. 1, 2025

Language: Английский

Citations

1
Recent advances in hydrofunctionalisation of cyclopropenes via carbon–heteroatom bond formation DOI
Jorge García‐Lacuna, Gema Domı́nguez, Ángel Manu Martínez

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review highlights recent advances in the hydrofunctionalisation of cyclopropenes through formation carbon–heteroatom bonds for synthesis polysubstituted cyclopropanes.

Language: Английский

Citations

1
Recent Advances in Transition Metal-Catalyzed C—Si Bond Cleavage of Silacyclobutanes DOI Open Access
Min Liu, Liping Qi, Dongbing Zhao

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(10), P. 3508 - 3508

Published: Jan. 1, 2023

Due to the widespread application of various organosilicon compounds in material science, electronic devices and pharmaceutical research, it is great significance develop green efficient synthetic methods for diverse silicon-containing molecules.Silacyclobutane an important kind small-membered rings, which exhibits unique reactivities under transition metal catalysis cleave C-Si bond driven by inherent ring strain Lewis acidity.The resulting Si-M species can then be transformed into compounds.Herein, recent advances Pd, Rh, Ni-catalyzed cleavage reactions silacyclobutanes are summarized detail, mechanism development tendency such briefly discussed.

Language: Английский

Citations

16
Tunable Regiodivergent Reactivity of N-Allenamides with Silacyclobutanes via Palladium Catalysis in the Synthesis of Silacyclic β-Aminosilanes DOI
Yidong Wang, Yan Sun, Tianying Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(14), P. 10882 - 10892

Published: July 4, 2024

The key structure of β-aminosilanes has attracted significant interest because their latent biological activities in the field medicinal chemistry. However, structural variety been significantly constrained by absence a comprehensive synthetic approach. Thus, development regiodivergent catalytic systems for construction structurally diverse via an intermolecular cycloaddition strategy would represent addition to limited toolkit available synthesis. We herein present attractive approach synthesis through regioselective N-allenamides with expansion silacyclobutanes catalyzed Pd/PR3. Just selecting suitable protecting group N-allenamides, regioselectivity is completely switched efficiently provide two regioisomers silacyclic β-aminosilanes. Two regioselectivities were proceeded during migratory insertion and reductive elimination process, origin which could be well rationalized using density functional theory calculations.

Language: Английский

Citations

6
Synthesis of Difluorocyclopropanes via Visible‐Light‐Mediated [1+2] Cycloaddition of Diazo Esters with gem‐Difluoroalkenes and Evaluation of their Antifungal Activity DOI
Donghua Du, Chang Ji,

Shaoying Zheng

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1738 - 1743

Published: Feb. 17, 2024

Abstract In this work, we reported a method for construction of difluorocyclopropanes through visible light‐promoted [1+2] cycloaddition reaction aryl diazo esters with gem ‐difluoroalkenes. The proceeds under mild conditions, encompasses wide range substrates (36 examples), exhibits good tolerance to various substituents, and demonstrates diastereoselectivity >20:1. Additionally, antifungal activity evaluation revealed that these derivatives exhibited certain activity, the EC 50 values products towards Botrytis cinerea Rhizoctonia solani were measured be 1.51 1.36 μM, respectively, which are significantly lower than those commercial fungicides Hymexazol Azoxystrobin. This work not only provides an efficient synthesis difluorocyclopropanyl derivatives, but reveals their potential applications in fungicide creation.

Language: Английский

Citations

5
Biocatalytic Enantioselective Reduction of Cyclopropenyl Esters and Ketones Using Ene-Reductases DOI
Tomohiro Yasukawa,

Pierre Gilles,

Juliette Martin

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 6188 - 6193

Published: April 8, 2024

Enantioselective reduction of cyclopropenyl esters and ketones to optically active cyclopropanes has been achieved by using whole-cell-overexpressing ene-reductases (EREDs). By these enzymes, trans-cyclopropanes were isolated in good yield high enantiomeric excess. A wide range cyclopropane obtained, a variety substituent patterns on the cyclopropenes tolerated.

Language: Английский

Citations

5
Theoretical study of an N-heterocyclic carbene-catalyzed annulation reaction between an enal and a β-silyl enone: Mechanism and origin of stereoselectivity DOI
Yang Wang,

Yilu Luo,

M. Zhao

et al.

Molecular Catalysis, Journal Year: 2023, Volume and Issue: 551, P. 113621 - 113621

Published: Oct. 27, 2023

Language: Английский

Citations

11