Enantioselective Rh(I)-Catalyzed C–H Arylation of Ferroceneformaldehydes DOI Creative Commons
Chen‐Xu Liu,

Fangnuo Zhao,

Qing Gu

et al.

ACS Central Science, Journal Year: 2023, Volume and Issue: 9(11), P. 2036 - 2043

Published: Sept. 28, 2023

As an important class of platform molecules, planar chiral ferrocene carbonyl compounds could be transformed into various functional groups offering facile synthesis ligands and catalysts. However, developing efficient straightforward methods for accessing enantiopure compounds, especially ferroceneformaldehydes, remains highly challenging. Herein, we report a rhodium(I)/phosphoramidite-catalyzed enantioselective C–H bond arylation ferroceneformaldehydes. Readily available aryl halides such as iodides, bromides, even chlorides are suitable coupling partners in this transformation, leading to series ferroceneformaldehydes good yields excellent enantioselectivity (up 83% yield >99% ee). The aldehyde group diverse smoothly, Ugi's amine PPFA analogues synthesized efficiently. latter was found ligand Pd-catalyzed asymmetric allylic alkylation reactions. Mechanistic experiments supported the formation imine intermediates key step during reaction.

Language: Английский

Mechanisms of C(sp3)–H and C=C selective oxidative heterofunctionalizations by non-heme Fe and Mn mimics of oxygenase enzymes DOI
Konstantin P. Bryliakov

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 508, P. 215793 - 215793

Published: March 18, 2024

Language: Английский

Citations

9
Enantioselective Synthesis of Indole-Fused Polycycles Bearing Four Consecutive Stereocenters via Rhodium Catalysis DOI
Ting Yu, Weiqi Liu, Beijing Chen

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Indole-fused polycycles are common in natural products and bioactive molecules, yet their concise efficient synthesis remains challenging, especially for compounds with multiple stereocenters. Herein, we report the application of a chiral CpxRhIII catalyst enantioselective C–H activation/[4+2] annulation indoles bicyclic alkenes. This catalytic system exhibits high enantioselectivity broad functional group tolerance operates under benign conditions. The scope this methodology encompasses variety substrates, delivering novel polycyclic four consecutive stereocenters bridged ring good to excellent yields remarkable enantioselectivities (≤1:99 er). approach facilitates structurally diverse molecules that retain integrity while introducing chirality. More importantly, 3ab significantly inhibited proliferation CESS Kasumin-1 cells IC50 values 0.76 0.28 μM, respectively. In addition, has been demonstrated as an effective agent promoting apoptosis cells.

Language: Английский

Citations

1
Enantioselective synthesis of indenols via rhodium(III)–catalyzed C-H activation/annulation of ketones with alkynes DOI

Bo-Bo Gou,

Wenjie Shen, Yuanjun Gao

et al.

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

Published: Feb. 12, 2025

Language: Английский

Citations

1
Recent advances in catalytic asymmetric alkenyl C(sp2)–H bond functionalizations DOI Creative Commons

Xiao‐Ju Si,

Tian-Ci Wang,

Teck‐Peng Loh

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review summarizes recent advances in asymmetric alkenyl C–H bond functionalization reactions, as well provides an outlook on future opportunities and challenges.

Language: Английский

Citations

1
Rhodium(III)-Catalyzed Atroposelective Indolization to Access Planar-Chiral Macrocycles DOI

Hongxuan Zhai,

Kang Lv, Jiayan Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 29214 - 29223

Published: Oct. 9, 2024

Macrocycles incorporating conformationally defined indoles are widely found in bioactive natural products. However, the catalytic enantioselective synthesis of planar-chiral via indolization involving macrocyclization remains elusive. Herein, we present first rhodium(III)-catalyzed atroposelective macrocyclization, which involves C-H activation aniline, and a subsequent oxidation [3 + 2] annulation reaction with an intramolecular alkyne. This protocol achieves construction indoles, planar chirality control single step. Importantly, this strategy produces macrocyclic atropisomers bearing full-carbon ansa chains, represent challenging targets organic synthesis. Thermodynamic experiments revealed that rotational barrier chain-linked atropisomer was lower than oxa-ansa chain. The mechanism elucidated by computational studies, alkyne insertion steps collectively determined enantioselectivity.

Language: Английский

Citations

8
Lead-halide perovskite quantum dots embedded in mesoporous silica as heterogeneous photocatalysts combined with organocatalysts for asymmetric catalysis DOI
Hao Ren, Yiming Li, Wenjing Li

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(10), P. 6068 - 6077

Published: Jan. 1, 2024

CsPbBr 3 quantum dots embedded in KIT-6 to form silica-shell-protected heterogeneous photocatalysts, which were further combined with chiral organocatalysts forming dual-catalysts explore the activity and stereoselectivity asymmetric catalysis.

Language: Английский

Citations

7
Electrochemical Enantioselective C–H Annulation by Achiral Rhodium(III)/Chiral Brønsted Base Domino Catalysis DOI Creative Commons
Yanjun Li, Jiawei Xu, João C. A. Oliveira

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8160 - 8167

Published: May 10, 2024

Rhodium(III)-catalyzed enantioselective C–H activation has emerged as a powerful tool for assembling enabling chiral molecules. However, this approach is significantly hampered by the cumbersome synthetic routes preparing rhodium catalysts. In sharp contrast, we herein report on an electrochemical domino catalysis system that exploits achiral Cp*-rhodium catalyst along with easily accessible Brønsted base activation/annulation reaction of alkenes benzoic acids. Our strategy offers environmentally benign and most user-friendly synthetically useful phthalides in good enantioselectivity, employing electricity sustainable oxidant.

Language: Английский

Citations

7
Copper-catalysed asymmetric annulation of yne-allylic esters with amines to access axially chiral arylpyrroles DOI Creative Commons

Chaochao Yao,

Danran Li,

Hua-Ming Xiang

et al.

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

Published: Aug. 10, 2024

The construction of atropisomers with 1,2-diaxes, while maintaining high enantiocontrol, presents a significant challenge due to the dynamic nature steric hindrance at ortho-aryl substituents. Although various catalytic asymmetric methods have been developed for accessing axially chiral arylpyrroles, synthesis arylpyrroles 1,2-diaxes in manner has remained rare. Herein, authors report diverse and C-C C-N axes through copper-catalysed asymmetirc [4 + 1] annulation yne-allylic esters arylamines via remote stereocontrol strategy. This approach provides facile access broad range heterobiaryl (67 examples) excellent enantioselectivities, each bearing one or two C-C/C-N axes, demonstrating its versatility efficiency. utility this methodology is further highlighted by transformation product into phosphine ligand, thioureas use catalysis.

Language: Английский

Citations

7
Application of Sulfoxonium Ylides or Iodonium Ylides in Rhodium‐Catalyzed Synthesis of Phenanthrenes DOI
Xiao Liu, Bingxin Zhou, Kelu Yan

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1744 - 1750

Published: Feb. 22, 2024

Abstract The transmetalation triggered rhodium‐catalyzed C−H bond activation and tandem annulation of 2‐biphenylboronic acids with sulfoxonium ylides or iodonium has been developed. Various products phenanthrenes were constructed under redox‐neutral conditions in 34–86% yields. Several mechanism exploration experiments derivatization reactions conducted sequence to gain a deeper understanding the process potential this transformation. It offers an alternative approach for synthesis phenanthrene derivatives.

Language: Английский

Citations

6
Palladium‐Catalyzed Atroposelective Kinetic C−H Olefination and Allylation for the Synthesis of C−B Axial Chirality DOI Open Access
Jie Xu, Weihua Qiu, Xu Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Oct. 16, 2023

Abstract The direct C−H functionalization of 1,2‐benzazaborines, especially asymmetric version, remains a great challenge. Here we report palladium‐catalyzed enantioselective olefination and allylation reactions 1,2‐benzazaborines. This approach is kinetic resolution (KR), providing various C−B axially chiral 2‐aryl‐1,2‐benzazaborines 3‐substituted in generally high yields with excellent enantioselectivities (selectivity (S) factor up to 354). synthetic potential this reaction showcased by late‐stage modification complex molecules, scale‐up reaction, applications.

Language: Английский

Citations

16