Article
Chemistry, Multidisciplinary
Jiaqing Lu, Yan Yao, Liubo Li, Niankai Fu
Summary: The direct decarboxylative alkenylation of widely available aliphatic carboxylic acids with vinyl halides has been achieved using Ce/Ni dual transition metal electrocatalysis. This reaction allows for the synthesis of alkenes with all substitution patterns and has a broad scope with respect to both coupling partners. The reaction can readily utilize simple primary alkyl carboxylic acids as carbon-centered radical precursors. Mechanistic studies have been conducted to understand the key intermediates and pathway of the reaction using controlled experiments and cyclic voltammetry data.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Changhua Song, Hong-Hao Zhang, Shouyun Yu
Summary: In this study, a decarboxylative allylic benzylation catalyzed by Pd/photoredox in a regio- and enantioselective manner is achieved. This method uses readily available aryl acetic acids as benzylic nucleophile equivalents without preactivation. The mild and atom-economical protocol expands the scope of coupling partners of allylic electrophiles. Additionally, vinyl epoxides can undergo this transformation smoothly, producing various chiral homoallylic alcohols bearing all-carbon quaternary stereocenters.
Article
Chemistry, Multidisciplinary
Alex M. Davies, Rafael D. Hernandez, Jon A. Tunge
Summary: A dual catalytic procedure involving photoredox and cobalt catalysts has been developed for the benzoylation of olefins. The photoredox catalyst initiates the decarboxylation of alpha-ketoacids to generate benzoyl radicals, which react with styrenes in the presence of a cobalt catalyst that abstracts a hydrogen atom. The catalytic system allows a Heck-like aroylation without the need for a stoichiometric oxidant. Mechanistic studies show that differently substituted styrenes result in a curved Hammett plot, suggesting a change in the product-determining step in the catalytic mechanism.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Yu Zhang, Jiahui Qian, Miao Wang, Yahao Huang, Peng Hu
Summary: An efficient and low-cost protocol for the direct decarboxylative fluorination of aliphatic carboxylic acids catalyzed by iron salts under visible light is presented. This new method is highly efficient and scalable, and mechanistic studies have revealed the generation process of the key step.
Article
Chemistry, Organic
Jean-Philippe Fontaine, Vincent Lapointe, Marion Filliatre, Guillaume Belanger
Summary: We present a novel green and metal-free method for the preparation of substituted indolines through photocatalyzed remote alkyl radical generation and cyclization. This method complements existing Fischer indolization, metal-catalyzed couplings, and photocatalyzed radical addition and cyclization. It allows for a wide range of functional groups, including aryl halides, which are incompatible with most existing methods. Electronic bias and substitution were investigated to achieve complete regiocontrol and high chemo-control in indoline formation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Jun Zheng, Christoph Nopper, Rifhat Bibi, Ali Nikbakht, Felix Bauer, Bernhard Breit
Summary: A dual photoredox/nickel catalyzed method for the regio- and diastereoselective allylation of N-aryl alpha-amino acids is presented. The reaction provides branched homoallylic amines in high yields and high syn-diastereoselectivity under mild and redox-neutral conditions. The broad substrate scope and high functional group tolerance demonstrate the synthetic flexibility of this reaction.
Article
Chemistry, Multidisciplinary
Jingjing Wu, Chao Shu, Zhihang Li, Adam Noble, Varinder K. Aggarwal
Summary: This article describes a visible-light photoredox-catalyzed decarboxylative halogenation reaction using inexpensive inorganic halide salts as halogenating agents. Bromination with lithium bromide can be achieved using an organic photoredox catalyst under simple conditions, while chlorination requires dual photoredox-copper catalysis. The reaction exhibits excellent functional group tolerance and can convert structurally complex natural products into alkyl bromides and chlorides. Additionally, the method is also applicable to thiocyanation reactions with potassium thiocyanide for the synthesis of alkyl thiocyanates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Mingxiang Zhu, Samir Messaoudi
Summary: This study presents a simple route for the synthesis of alkynyl C-nucleosides using low-cost and nontoxic copper catalysis, demonstrating the power of Cu/photoredox dual catalysis in accessing highly complex glycosides under mild conditions.
Article
Multidisciplinary Sciences
Shuaishuai Wang, Tingrui Li, Chengyihan Gu, Jie Han, Chuan-Gang Zhao, Chengjian Zhu, Hairen Tan, Jin Xie
Summary: This article reports on an iron-catalyzed reaction for efficient construction of aromatic tertiary amines, which is important in drug discovery and organic chemistry. The reaction employs a radical tandem C-N coupling strategy and can synthesize nonsymmetric aromatic tertiary amines under mild conditions.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Xiaochuang Wang, Yi Li, Xuesong Wu
Summary: In this report, a photoredox/cobalt dual catalytic system was developed for the synthesis of distally unsaturated ketones. By using an organo photoredox catalyst and a cobaloxime catalyst in cooperation, sequential ring-opening C-C bond scission and dehydrogenation of nonstrained tertiary cycloalkanols of various ring sizes were achieved under visible-light irradiation, resulting in a wide range of distally unsaturated ketones with good yields and hydrogen gas as the only byproduct. The produced distally unsaturated ketones are versatile building blocks that can be easily converted to other valuable molecules.
Article
Chemistry, Applied
Palasetty Chandu, Debabrata Das, Krishna G. Ghosh, Devarajulu Sureshkumar
Summary: This study presents a visible-light mediated photoredox catalyzed decarboxylative alkylation of vinylcyclopropanes using an Ir-based photocatalyst and Cs2CO3 as a base. Long-chained alkylated derivatives were obtained in moderate to high yields under mild reaction conditions without the need for external metal co-catalysts, oxidants, or additives. Various alkyl carboxylic acids and amino acid derivatives were used as alkylating reagents to synthesize gamma,delta-unsaturated diesters and unnatural homo-allylic amino acid derivatives with excellent functional groups tolerance. The method was further validated through gram-scale synthesis and a proposed mechanism based on control experiments and quenching studies.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yonghong Xiao, Can-Ming Zhu, Rong-Bin Liang, Yong-Liang Huang, Chun-Hua Hai, Jian-Rui Chen, Mian Li, Jian-Ji Zhong, Xiao-Chun Huang
Summary: In this study, an unprecedented cobaloxime-based zirconium metal-organic framework (Zr-TCPCo) with a unique structure is designed and synthesized. As a photocatalyst, this material exhibits excellent catalytic activity for the aerobic oxidation of arylboronic acids to phenols. Recycling experiments demonstrate the stability and reusability of Zr-TCPCo as a robust catalyst.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Xiang Sun, Tobias Ritter
Summary: In this study, a novel method for polyfluoroarylation of aliphatic carboxylic acids was reported, with broad substrate scope and high functional group tolerance. Small complex molecules such as natural products and drugs can be modified through late-stage modification.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Qiao-Fei Bao, Ming Li, Yu Xia, Yu-Zhao Wang, Zhao-Zhao Zhou, Yong-Min Liang
Summary: The photocatalytic decarboxylative radical addition bifunctionalization cascade presented in this study relies on single-electron transfer to complete the catalytic cycle. The reaction offers advantages such as the use of commercially available materials, wide functional group compatibility, and mild conditions. Importantly, some amino acids and bioactive carboxylic acids can provide corresponding products in moderate to good yields, highlighting their potential value in drug development.
Article
Chemistry, Organic
Hui Xu, Hong Zhang, Qing-Xiao Tong, Jian-Ji Zhong
Summary: A dual-catalytic platform combining photoredox catalysis and cobaloxime catalysis was reported for the allylation of amines and sulfonyl hydrazines with olefins to selectively access alpha-allylic amines and allylic sulfones in good yields. The strategy avoided the use of a stoichiometric amount of terminal oxidant and pre-functionalized allylic precursors, presenting a green and ideal atom- & step-economical process. Mechanistic studies suggested the involvement of a radical process in this reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Amit Kumar, Chelsea G. Comadoll, Daniel S. King, Allen G. Oliver, Victor W. Day, James D. Blakemore
Summary: The synthesis of heterobimetallic complexes utilizing organometallic [Cp*M] fragments on the diimine-dioximato platform has been successfully demonstrated. The coordination of Rh(III) and Ir(III) centers by the nascent dioximato site allows for the installation of [Cp*M] fragments into metallomacrocycles, resulting in subtle influences on the properties of each metal in close proximity. Spectroscopic and electrochemical studies confirm the moderate M'·M distances in the modular compounds, highlighting the potential for further exploration in this synthetic chemistry.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Luis M. Mori-Quiroz, Chelsea G. Comadoll, Jonathan E. Super, Michael D. Clift
Summary: New methods for C-N bond construction utilizing the N-centered electrophilic character of iminoquinones have been reported. Various nitrogen-containing heterocycles can be synthesized under different reaction conditions, demonstrating the wide application of iminoquinones in organic synthesis.
Article
Chemistry, Inorganic & Nuclear
Chelsea G. Comadoll, Wade C. Henke, Julie A. Hopkins Leseberg, Justin T. Douglas, Allen G. Oliver, Victor W. Day, James D. Blakemore
Summary: [Cp*Rh] hydride complexes have been successfully synthesized and isolated using chelating diphosphine ligands, showing direct Rh-H interactions with characteristic infrared spectra frequencies. Comprehensive NMR experiments revealed unique spin systems and coupling patterns for these complexes, demonstrating a modular reduction/protonation reaction sequence for the preparation of diverse [Cp*Rh] monohydrides.
