Functionalization of Boranes through Thiol/Oxygen Catalysis† DOI Creative Commons

Hongyi Tao,

Hairong Lyu

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(22), P. 2804 - 2810

Published: July 17, 2024

Comprehensive Summary A greener and more convenient alternative to traditional methods for the generation of thiyl radical as hydrogen atom transfer (HAT) catalyst is developed, using molecular oxygen oxidize thiol without need chemical initiators or light irradiation. The thiol/oxygen catalysis enables selective efficient difunctionalization borane.

Language: Английский

Arenethiolate-Catalyzed 1,5-HAT of Aryl Halides: Synthesis of γ-Spirolactams DOI
Wei Xiao,

Shengyun Liu,

Yuhui Lin

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3081 - 3085

Published: April 3, 2024

γ-Spirolactam is a privileged building block that found in wide range of natural products and bioactive compounds. Herein, we report an arenethiolate-catalyzed 1,5-HAT aryl halides to obtain γ-spirolactams through SET reduction/intramolecular 1,5-HAT/cyclization/HAT process. This protocol features metal-free conditions broad substrate scope, furnishing the moderate excellent yields. Notably, bromides, chlorides even fluorides are well tolerated this transformation. A mechanism involving arenethiolate as catalyst proposed based on DFT calculation.

Language: Английский

Citations

6
Nature-Inspired Radical Pyridoxal-Mediated C–C Bond Formation DOI
Ye Wang, Soumik Das,

Kareem Aboulhosn

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23321 - 23329

Published: Aug. 6, 2024

Pyridoxal-5'-phosphate (PLP) and derivatives of this cofactor enable a plethora reactions in both enzyme-mediated free-in-solution transformations. With few exceptions each category, such chemistry has predominantly involved two-electron processes. This sometimes poses significant challenge for using PLP to build tetrasubstituted carbon centers, especially when the reaction is reversible. The ability access radical pathways paramount broadening scope catalyzed by coenzyme. In study, we demonstrate PLP-based intermediate engage number C-C bond-forming reactions. By selection an appropriate oxidant, single-electron oxidation quinonoid can be achieved, which subsequently applied Through pathway, synthesized series α-tertiary amino acids esters investigate substrate identify nonproductive pathways. Beyond acid model system, that other classes amine substrates range small molecule reagents serve as coupling partners semiquinone radical. We anticipate versatile species will central development novel

Language: Английский

Citations

5
Synthesis of Acylbenzo[b]thiophenes, Benzofurans and Indoles via Intramolecular Oxidative Cyclization Enabled by Photocatalytic Hydrogen Atom Transfer (HAT) DOI Creative Commons

Fen-Dou Wang,

Jin Jiang,

Tiantian Xu

et al.

Tetrahedron Chem, Journal Year: 2025, Volume and Issue: unknown, P. 100119 - 100119

Published: Jan. 1, 2025

An efficient strategy for intramolecular oxidative cyclization of 2-alkynylthioanisoles toward 3-acylbenzo[b]thiophenes by photochemical hydrogen atom transfer catalysis has been developed. 3-Acylbenzo[b]selenophenes, benzofurans and indoles can also be prepared this protocol. This reaction is convenient to perform at room temperature under simple conditions using air as the oxidant. Mechanistic studies revealed that formation α-thioalkyl radicals intermediate crucial.Graphical abstract

Language: Английский

Citations

0
Photocatalyzed Deuterodichloromethylation of Olefins Using Silacarboxylic Acids as Halogen‐Atom Transfer Reagents DOI Open Access

Xin‐Long Yu,

Jiawei Hu, Jian Cao

et al.

European Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Abstract A visible‐light‐induced deuterodichloromethylation of alkenes was developed with readily available and inexpensive deuterochloroform as the reagent. Silacarboxylic acids, which could generate silyl radicals through efficient decarboxylation, were applied halogen atom transfer agents. series deuterium‐containing gem ‐dichloroalkanes prepared in good yields.

Language: Английский

Citations

0
Photocatalytic Iminothiolation of Alkenes via Monothiocarbonate Oxime Esters DOI
Ranjini Laskar,

Rebecca E. Thielemann,

Janosch Knüppe

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6731 - 6738

Published: April 10, 2025

Language: Английский

Citations

0
C–F Activation of Fluorinated Esters Using Photocatalytically Generated Diaminoalkyl Radical DOI

Vladislav S. Kostromitin,

Artem O. Sorokin,

Vitalij V. Levin

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(35), P. 6598 - 6602

Published: Aug. 29, 2023

A method for hydrofluoroalkylation of alkenes with trifluoroacetic esters under visible light irradiation affording difluorinated products is described. The reaction involves readily available trimethyltriazinane as a shoichiometric reducing agent, which generates diamino-substituted alkyl radical serving strong electron donor. It believed that the cleavage C–F bond by triazinane-derived single reduction coupled fluoride transfer.

Language: Английский

Citations

10
Practical photocatalytic hydroalkylation of alkenes with chloroacetates mediated by the formate ion DOI

Ekaterina V. Malakhova,

Vladislav S. Kostromitin,

Vitalij V. Levin

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(10), P. 2829 - 2833

Published: Jan. 1, 2024

Commodity chemicals are used as alkylating and reducing agents for radical addition to alkenes. The method is based on activation of the strong C–Cl bond by anion carbon dioxide.

Language: Английский

Citations

3
Peptide macrocyclisation via intramolecular interception of visible-light-mediated desulfurisation DOI Creative Commons

Frances R. Smith,

Declan Meehan,

Rhys C. Griffiths

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(25), P. 9612 - 9619

Published: Jan. 1, 2024

Herein, we report a peptide cyclisation strategy via intramolecular interception of cysteine desulfurisation. This method enables the unprotected peptides in aqueous solution installation hydrocarbon linkage.

Language: Английский

Citations

3
Photocatalyzed dehalogenative deuteration with silacarboxylic acids as halogen-atom transfer agents DOI
Jiawei Hu, Jian Cao, Li‐Wen Xu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 4757 - 4761

Published: Jan. 1, 2024

A visible light-induced organophotocatalytic strategy for dehalogenative deuteration of a wide variety primary, secondary, and tertiary alkyl bromides is reported.

Language: Английский

Citations

2
Recent Advances in the Application of Carbon Dioxide Radical Anion DOI
Jing Hou, Yan Huang, Hao Li

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(10), P. 3117 - 3117

Published: Jan. 1, 2024

Language: Английский

Citations

2