Asymmetric synthesis of β-amino acid derivatives by stereocontrolled C(sp3)-C(sp2) cross-electrophile coupling via radical 1,2-nitrogen migration DOI Creative Commons
Shi Tang,

Zi-Cheng Liao,

Mengwu Xiao

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Abstract Optically pure non-natural β-amino acids are noteworthy molecular motifs of numerous pharmaceutically important molecules. Skeletal editing abundant α-amino acid scaffolds via tandem radical 1,2-N-shift/cross-coupling represents an attractive and powerful tool to straightforward assemble new molecules; however, this strategy presents substantial challenges owing difficulties in reactivity regio-/enantiocontrol. Herein, we report unprecedented remote cross-electrophile C(sp2)-C(sp3) coupling β-bromo esters with aryl bromides a π-system-independent 1,2-N-shift, which allows access α-arylated β-amino high efficiency regioselectivity. Furthermore, upon the novel cooperative catalysis Ni(II)/new-style Box complex chiral phosphoric (CPA), migratory further achieves enantioselectivity control C(sp3)–C(sp2) bond construction. In addition, detailed experimental studies DFT calculations were conducted gain insight into mechanism origin enantioselectivity, was evidenced by two-step synthesis pan-Akt inhibitor molecule. Overall, synergistic expands these methods challenging enantioselective C(sp2)–C(sp3) 1,2-amino migration.

Language: Английский

Photoinduced Copper‐Catalyzed Three‐Component Radical Carboamination of Styrene Derivatives DOI Open Access

Xiao-Die Huan,

Juan Zhang,

Wenjing Xiao

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(23)

Published: Aug. 28, 2024

Abstract The catalytic three‐component radical carboamination of alkenes has recently emerged as an alternative and robust platform for the rapid construction diverse valuable amines. Despite great advances in this field, new methods that enable highly selective access to chemical space surrounding amine functional groups are still high demand. Herein, we report a generally applicable visible light‐induced copper‐catalyzed cyanoalkylamination reaction alkenes, oxime carbonates, benzoyloxycarbamates. This protocol demonstrates chemo‐selectivity, broad substrate scope, good group tolerance, providing variety cyanoalkylated aliphatic amines with yields.

Language: Английский

Citations

0
Solvent‐Free Synthesis of Carvone Oxime Ester and Carvone Oxime Sulfonic Esters DOI Open Access
Hao Yang,

Guanxiong Yan,

Guo Zeng

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(38)

Published: Oct. 1, 2024

Abstract A ZnO‐mediated benzoylation between carvone oxime and acyl is reported, enabling access to diverse ester sulfonic esters under solvent‐free conditions. The operationally simple procedure provides a novel method for the synthesis of oxime‐ester bonds with excellent chemo selectivity. This strategy mild, direct, green approach synthesizing in moderate yields good substrate tolerance. In addition, was synthesized

Language: Английский

Citations

0
Theoretical Exploration of Siloxy Carbenes: Photogeneration and [2+1] Photocyclization Mechanisms DOI

Jianhao Li,

Xiaohan Jiang, Zhongmin Liang

et al.

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Regulatory mechanisms for the photogeneration of singlet/triplet siloxy carbenes and their involvement in [2+1] photocyclizations have been thoroughly studied at CASPT2//CASSCF/PCM level theory.

Language: Английский

Citations

0
Paired Electro‐Synthesis of Remote Amino Alcohols with/in H2O DOI
Zhixiong Ruan,

Xinyue Fang,

Xinwei Hu

et al.

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

Published: Nov. 13, 2024

Abstract Amino alcohols, particularly remote amino alcohols and peptide are valuable due to their functional diversity in biologically active compounds. However, traditional synthesis methods face significant challenges, making electrochemistry an attractive alternative. We have developed a mild biocompatible sequential paired electrolysis strategy, leveraging copper‐electrocatalysis synthesize diverse including unnatural alcohols. Both experimental results density theory (DFT) calculations demonstrated that water serves as both the hydroxyl source solvent, facilitating generation of CuH with Cu(I) at cathode, which turn reduces aldehyde intermediates formed during reaction.

Language: Английский

Citations

0
Asymmetric synthesis of β-amino acid derivatives by stereocontrolled C(sp3)-C(sp2) cross-electrophile coupling via radical 1,2-nitrogen migration DOI Creative Commons
Shi Tang,

Zi-Cheng Liao,

Mengwu Xiao

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Abstract Optically pure non-natural β-amino acids are noteworthy molecular motifs of numerous pharmaceutically important molecules. Skeletal editing abundant α-amino acid scaffolds via tandem radical 1,2-N-shift/cross-coupling represents an attractive and powerful tool to straightforward assemble new molecules; however, this strategy presents substantial challenges owing difficulties in reactivity regio-/enantiocontrol. Herein, we report unprecedented remote cross-electrophile C(sp2)-C(sp3) coupling β-bromo esters with aryl bromides a π-system-independent 1,2-N-shift, which allows access α-arylated β-amino high efficiency regioselectivity. Furthermore, upon the novel cooperative catalysis Ni(II)/new-style Box complex chiral phosphoric (CPA), migratory further achieves enantioselectivity control C(sp3)–C(sp2) bond construction. In addition, detailed experimental studies DFT calculations were conducted gain insight into mechanism origin enantioselectivity, was evidenced by two-step synthesis pan-Akt inhibitor molecule. Overall, synergistic expands these methods challenging enantioselective C(sp2)–C(sp3) 1,2-amino migration.

Language: Английский

Citations

0