Construction of Sulfur(IV)‐Chiral Six‐Membered Heterocycles by Pd‐Catalyzed Asymmetric (4+2) Dipolar Cyclization DOI

Fen‐Ya Xiong,

Sudip Pan,

Bao‐Cheng Wang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Abstract Chiral sulfur‐containing compounds play an important role in asymmetric catalysis and synthesis, chiral pharmaceuticals, materials. While great progress has been made the synthesis of these compounds, catalytic heterocycles remains relatively limited compared to acyclic ones. In this study, we successfully report efficient highly selective structurally diverse chirality‐at‐sulfur(IV) six‐membered under mild conditions via a Pd‐catalyzed (4+2) dipolar cyclization. More importantly, products enable enantioselective preparation variety other S‐stereogenic derivatives.

Language: Английский

Electrochemical enabled cobalt catalyzed enantioselective C-H acyloxylation of aryl phosphamide with carboxylic acid DOI

Xuying Xia,

Changdi Zheng,

Yunfei Hang

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(14), P. 8323 - 8329

Published: Jan. 1, 2024

We described here the first example of cobalt-electro-catalyzed enantioselective C–H acyloxylation arylphosphinamides with carboxylic acids to generate P-stereogenic scaffolds.

Language: Английский

Citations

9
Chemodivergent and Enantioselective Synthesis of Spirobi[dihydrophenalene] Structures DOI

Peng Chuan-yong,

Chenhong Wang, Changhui Wu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(3), P. 869 - 873

Published: Jan. 10, 2025

The development and enantioselective synthesis of two types C2-symmetric spirobi[dihydrophenalene] structures is reported. reaction proceeds via rhodium-catalyzed 2-fold asymmetric conjugate arylation dienones followed by BF3·OEt2-promoted spirocyclization to give the enantiopure spiro products. Additive-dependent chemodivergent 3,3'-diarylated 2,2',3,3'-tetrahydro-1,1'-spirobi[phenalene]-9,9'-diols (3,3'-Ar2-SPHENOLs) corresponding diary ethers from same intermediate achieved. structural properties 3,3'-Ph2-SPHENOL are analyzed, its application in catalysis has been preliminarily demonstrated.

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
Parametrization of κ2-N,O-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations DOI Creative Commons
Suman Dana, Neeraj Kumar Pandit, Philipp Boos

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4450 - 4459

Published: Feb. 28, 2025

Enantioselective electrocatalyzed C–H activations have emerged as a transformative platform for the assembly of value-added chiral organic molecules. Despite recent progress, construction multiple C(sp3)-stereogenic centers via C(sp3)–C(sp3) bond formation has thus far proven to be elusive. In contrast, we herein report an annulative activation strategy, generating Fsp3-rich molecules with high levels diastereo- and enantioselectivity. κ2-N,O-oxazoline preligands were effectively employed in enantioselective cobalt(III)-catalyzed reactions. Using DFT-derived descriptors regression statistical modeling, performed parametrization study on modularity preligands. The resulted model describing ligands' selectivity characterized by key steric, electronic, interaction behaviors.

Language: Английский

Citations

1
Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence DOI Creative Commons
Tristan von Münchow, Neeraj Kumar Pandit, Suman Dana

et al.

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Language: Английский

Citations

1
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
Electrocatalytic Cascade Selenylation/Cyclization/Deamination of 2-Hydroxyaryl Enaminones: Synthesis of 3-Selenylated Chromones under Mild Conditions DOI

Kaili Cen,

Yuan Liu,

Junhong Yu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 8632 - 8640

Published: June 6, 2024

Herein, we disclosed a highly efficient pathway toward 3-selenylated chromone derivatives via electrocatalytic cascade selenylation/cyclization/deamination of 2-hydroxyaryl enaminones with diselenides. This method showed mild conditions, easy operation, wide substrate scope, and good functional group tolerance. Furthermore, this electrosynthesis strategy was amendable to scale-up the reaction. Additionally, preliminary experiments revealed that reaction probably proceeded cation instead radical pathway.

Language: Английский

Citations

6
Catalytic Asymmetric C–H Activation/Cyclization of Sulfoximines with Sulfoxonium Ylides by a Chiral η6-Benzene Ruthenium(II) Catalyst DOI
Huan Liu, Ji‐Jun Jiang, Jun Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17398 - 17404

Published: Nov. 12, 2024

Chiral η6-benzene ruthenium(II) (BenRuII)-catalyzed asymmetric C–H activations are challenging and rarely seen in the literature. Herein, activation/cyclization of sulfoximines with sulfoxonium ylides catalyzed by chiral BenRuII catalyst derived from (S)-H8–BINOL is described. It provides efficient access to various sulfur-chiral 1,2-benzothiazine 1-oxides high yields enantioselectivities (up 99% yield 98% ee). Kinetic resolution racemic was also feasible. The reaction mechanism studied tool H/D exchange kinetic isotope effect. metallacycle revealing origin induction prepared, characterized, proved effective for model reaction. This work demonstrates great potential catalysts activation.

Language: Английский

Citations

5
Electrocatalytic Enantioselective Tandem C–H Indolization toward Biindolyl Atropisomers: Reaction Development and Mechanistic Insight DOI

Zhi‐Huan Peng,

Ping Huang, Ao-Long Li

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1422 - 1430

Published: Jan. 9, 2025

The electrochemical methods for asymmetric indolization are still elusive and pose a significant challenge. Taking advantage of 2-alkynylanilines as electrochemically compatible indolyl equivalents, we herein represent mild highly enantioselective electrocatalytic process tandem C–H to form 2,3′-biindolyl atropisomers along with hydrogen evolution reaction. Integrated experimental computational mechanistic studies revealed that sequential metalation/nucleophilic cyclization/reductive elimination/anodic oxidation sequence involving RhIII–RhI–RhIII catalytic cycle accounts the established transformation.

Language: Английский

Citations

0
Electrochemical N–H Methylsulfoxidation of Sulfoximines with DMSO DOI Open Access

Qing‐Ru Zhu,

Gen Liu, Yongxiang Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Comprehensive Summary The N–H methylsulfoxidation of sulfoximines using DMSO as a methylsulfinyl source, induced by electrochemistry, has been developed. This method is the first example an electrochemical reaction in which serves source. Unlike previous reactions involving substrate, exclusively proceed via radical mechanisms, this follows S‐cation pathway. A wide range N ‐methylsulfinyl were successfully obtained.

Language: Английский

Citations

0