Article
Chemistry, Multidisciplinary
Mahesh Puthanveedu, Vladislav Khamraev, Lukas Brieger, Carsten Strohmann, Andrey P. Antonchick
Summary: A transition-metal-free direct electrolytic C-H amination involving an electrochemically generated nitrenium ion intermediate has been developed. The electrosynthesis takes place in the absence of any organoiodine catalysts and is enabled by an in situ generated electrolyte. A novel, efficient intramolecular and intermolecular C-H amination has been demonstrated using a simple reaction setup.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Eisuke Sato, Ayaka Yukiue, Koichi Mitsudo, Seiji Suga
Summary: Anodic oxidation was used to achieve the aromatization of 1,2,3,4-tetrahydrocarbazoles. Nitrogen-protected tetrahydrocarbazoles were converted to carbazoles with the use of bromide as a mediator. The presence of AcOH and the inexpensive bromide source LiBr allowed for efficient transformation.
Article
Chemistry, Multidisciplinary
Chong Huang, Zhao-Yu Li, Jinshuai Song, Hai-Chao Xu
Summary: This paper presents a catalyst- and reagent-free formal aza-Wacker type cyclization reaction for the synthesis of functionalized saturated N-heterocycles, conducted in a continuous-flow electrochemical reactor. The reactions exhibit broad tolerance of di-, tri-, and tetrasubstituted alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jessica C. Bieniek, Boris Mashtakov, Dieter Schollmeyer, Siegfried R. Waldvogel
Summary: This study presents an electrocatalytic method using hypervalent iodine(III) as a mediator to synthesize 1H-N-aryl-3,4-dihydroquinolin-2-ones by C-N bond formation. The method features a low catalyst loading, recycling of the solvent, and is a sustainable alternative to conventional approaches.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Santanu Ghosh, Yongxiang Zheng, Daniele Maccarone, Feven-Alemu Korsaye, Ilaria Ciofini, Laurence Miesch
Summary: A green and mild synthetic pathway was used to prepare a new class of ynamides for the environmentally friendly synthesis of benzo-1,5 dioxocines. The propargylic ynamides were transformed into eight-membered heterocycles fused to aryl groups through the addition of enolates to N-allenamide ethers. The regioselective proximal O-alkylation on the N-allenamide provided shelf-stable eight-membered heterocycles substituted by an amide, significantly expanding the chemical space of benzo-1,5 dioxocines.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Multidisciplinary Sciences
Junli Chao, Yuanyuan Yue, Ke Wang, Xiaohui Guo, Chunying Sun, Yue Xu, Jianming Liu
Summary: A concise copper-catalyzed oxidative dehydrogenative dearomatization method was developed for the direct synthesis of spirocyclic indolenines containing fluorene and indeno[2,1-b]indole groups. The utility of this method was demonstrated by achieving dual oxidative dehydrogenative dearomatization and producing the desired spirocyclic indolenines with fluorene groups. Mechanistic analyses revealed that the C-H cleavage of the phenyl ring was not involved in the rate-limiting step.
Article
Chemistry, Organic
Xiao-De An, Da-Ying Shao, Bin Qiu, Jian Xiao
Summary: An unprecedented cross-dehydrogenative coupling reaction of two C(sp(3))-H bonds to form ninemembered rings via hydride transfer has been developed. This methodology offers atom and step economy, metal-free and redox-neutral conditions, and water as the byproduct, making it applicable even with decomposed aldehydes.
Article
Chemistry, Organic
Xiao-De An, Da-Ying Shao, Bin Qiu, Jian Xiao
Summary: An unprecedented hydride transfer-triggered cross-dehydrogenative coupling of two C(sp(3))-H bonds to target nine membered rings has been developed. Salient features of this methodology include atom and step economy and metal-free and redox-neutral conditions, with water as the byproduct and proceeding well even with decomposed aldehydes.
Article
Chemistry, Organic
Jae-Hwan Kwak, Yohan Park, Jee Eun Hong, Jisong Yoon, Woohyun Baek, Kyumin Kim
Summary: Here, we describe a direct electrochemical C(sp3)-H lactonization of 2-alkylbenzoic acids for the synthesis of phthalides. This reaction utilizes a graphite anode, dichloromethane (DCM) solvent, hexafluoroisopropanol (HFIP) cosolvent, and n-Bu4NClO4 electrolyte to provide a wide substrate scope of 2-alkylbenzoic acids bearing primary to tertiary C(sp3)-H bonds. Our synthetic approach offers a simple, intuitive, and atom-economical protocol for the synthesis of various phthalides (25 examples, up to 92% yield) and other 5-and 6-membered lactones (10 examples, up to 83% yield).
Article
Chemistry, Multidisciplinary
Congjun Yu, Raolin Huang, Frederic W. Patureau
Summary: This article introduces a novel non-directed dehydrogenative phenone coupling method between methylarenes and aromatic C_H bonds, which exhibits a broad substrate scope and can be applied for gram-scale synthesis of drug analogues.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Raffaella Mancuso, Patrizio Russo, Melania Lettieri, Domenico Santandrea, Corrado Cuocci, Bartolo Gabriele
Summary: Polycyclic heterocyclic derivatives can be synthesized in one step by a carbonylative double cyclization approach, with yields ranging from 45% to 86%, showing promising potential for various applications.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Kunlayanee Punjajom, Sureeporn Ruengsangtongkul, Jumreang Tummatorn, Praneet Paiboonsombat, Somsak Ruchirawat, Charnsak Thongsornkleeb
Summary: A general protocol for oxidative annulation was developed to prepare 2-methyl-3,4-diacylquinolines directly from 2-alkynylanilines and 1,3-ketoesters. The reactions were mediated by Mn(OAc)3 in acetic acid at room temperature, leading to the desired quinoline products in one-pot in low to good overall yields on a wide range of substrates. The current method is convenient, conducted under mild conditions, and has short reaction times.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Youyoung Kim, Dongwook Kim, Sukbok Chang
Summary: An iridium(III)-catalyzed electrooxidative intramolecular dehydrogenative C-H/N-H coupling of unprotected 2-alkenyl anilines is described, allowing the synthesis of various 3-substituted N-H indole scaffolds under undivided electrolytic conditions. Mechanistic studies indicate that the reaction proceeds through an electro-oxidation induced reductive elimination pathway.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Alexis Tabey, Pooja Y. Vemuri, Frederic W. Patureau
Summary: The high electronegativity of nitrogen presents challenges for N-N bond forming cross-coupling reactions, especially in an intermolecular fashion. Dehydrogenative N-N coupling reactions are advantageous in terms of step and atom economy, but require careful design of an oxidizing system to avoid unwanted side reactions. Despite the importance of N-N bonds in organic chemistry, only a few intermolecular hetero N-N cross-dehydrogenative couplings exist, highlighting the need for further research in this area.
Article
Chemistry, Organic
Yan Hu, Jiang Nan, Jiacheng Yin, Guanjie Huang, Xin Ren, Yangmin Ma
Summary: A novel Rh-catalyzed C-H/C-H alkenylation of N-arylmethanimines with vinylene carbonate has been reported, giving access to C3,C4-nonsubstituted quinolines. This process is simple, requires lower catalyst loading, and allows for postfunctionalization with bioactive molecules.
Article
Chemistry, Organic
Jun Xu, Chao Peng, Bolin Yao, Hua-Jian Xu, Qiang Xie
Summary: This report describes a method for the deoxyfluorination of alcohols using KF as the fluorine source via in situ generation of highly active CF3SO2F. Diverse functionalities, including halogen, nitro, ketone, ester, alkene, and alkyne, are well tolerated. The mild conditions, short reaction time, and wide substrate scope make this method an excellent choice for constructing C-F bonds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Lei Xu, Zheng Dong, Qi Zhang, Ning Deng, Shi-Yu Li, Hua-Jian Xu
Summary: This article introduces new methods for Miyaura borylation and protoboration of alkynes catalyzed by low loadings of palladium, which have a broad substrate scope, good functional-group compatibility, and gram-scale synthetic ability.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Fei Tang, Yi-Si Feng, Zhi-Fei Cheng, Qi Zhang, Hua-Jian Xu
Summary: We report a copper metallaphotocatalytic 1,2-difunctionalization of terminal alkynes with N-hydroxyphthalimide (NHP) esters and readily available silyl reagents (TMSCN and TMSNCS) to access stereodefined trisubstituted alkenes, including (E)-alkenyl nitriles and thiocyanates. The reaction proceeds with excellent anti-stereoselectivity and demonstrates broad compatibility with a wide range of terminal alkynes and NHP esters as alkyl radical precursors. Experimental and computational studies have been performed to gain insight into the reaction mechanism.
Article
Multidisciplinary Sciences
Jian-Jun Dai, Xianglin Yin, Lei Li, Mario E. Rivera, Ye-Cheng Wang, Mingji Dai
Summary: This study presents a modular and practical diamination of allenes, allowing for efficient syntheses of beta,gamma-diamino carboxylates and sulfones. The reaction exhibits broad substrate scope, excellent functional group tolerability, and scalability.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Jun Xu, Jia-Wei Liu, Rui Wang, Jian Yang, Kui-Kui Zhao, Hua-Jian Xu
Summary: The conversion of easily available trifluoromethylarenes through C-F bond activation provides a rapid pathway for accessing difluorobenzylic substructures, which is important in the production of pharmaceuticals and agrochemicals. However, the current advances in this field have been limited to the construction of C-C-(H) bonds, thus restricting the diversity of accessible motifs. The selective formation of a carbon-heteroatom bond via C-F bond functionalization remains a challenging synthetic task, but it enables the direct synthesis of medicinally interesting aryldifluoromethyl ether [ArCF2X- (X= S, O, or Se)] scaffolds.
Article
Chemistry, Organic
Jiwei Wu, Yuting Zhang, Jingyi Yang, Lingxiang Yu, Shaoqing Zhang, Jie Zhou, Zirong Li, Xiaolan Xu, Huajian Xu
Summary: A novel method for the synthesis of formamides through the decarboxylative N-formylation of amines with glyoxylic acid has been developed. This method provides an efficient protocol for the synthesis of various formamides with moderate to excellent yields, and it can accommodate a wide range of functional groups under metal free and base free conditions. Moreover, the large-scale experiments and high chemoselectivity have shown great potential application of this strategy.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wei Zhou, Zhi-Wen Luo, Hua Xiao, Jun Yi, Jian-Jun Dai
Summary: In this study, a photo-induced radical reaction was developed to convert vinylboronic esters into alkylboronic esters using CuCl2 as a catalyst. The method features mild reaction conditions, easily accessible reagents, and scalability for gram-scale synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Le Zhang, Ye Liu, Chao-Xu Li, Lei Zhu, Guo-Yin Xiong, Shi-Lu Fan, Jian-Jun Dai, Hua Xiao
Summary: A phosphine-promoted tandem Diels-Alder reaction using pentadienyl 4-nitrobenzoate as a diene precursor with 3-olefinic oxindoles or CF3-activated ketones as dienophiles has been developed. This method provides a metal-free and step-efficient approach for synthesizing exomethylene-bearing spirooxindoles and dihydropyrans, which are privileged structures found in natural products.
Article
Chemistry, Multidisciplinary
Wen Fang, Huai-Qin Wang, Wei Zhou, Zhi-Wen Luo, Jian-Jun Dai
Summary: In this study, a photoinduced, CuCl2 mediated C(sp(3))-H borylation of unactivated alkanes is reported. This method offers mild reaction conditions, readily available reagents, and gram-scale scalability.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Zheng Dong, Ren-Jie Tong, Lei Xu, Hua-Jian Xu, Jun Xu
Summary: The synthesis of (deuterated) 1,1-disubstituted alkenes via Pd-catalyzed decarboxylative hydroarylation of alkynyl carboxylic acids with arylboronic acids has been developed. The reaction features excellent regioselectivity, a broad substrate scope and gram-scale synthetic ability and offers a general synthetic method to synthesize 1,1-dideuterio olefins. Preliminary mechanism investigations indicate that 1,1-disubstituted alkenes are formed by hydroarylation of terminal alkynes generated by in situ decarboxylation of alkynyl carboxylic acids.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jun Xu, Li Liu, Zhao-Cheng Yan, Yang Liu, Long Qin, Ning Deng, Hua-Jian Xu
Summary: In this research, a photoredox-catalyzed hydroxyalkylation method was developed for azole derivatives with aldehydes in the aqueous phase under an air atmosphere. Additionally, the catalytic system was also suitable for the alkylation of azole derivatives with alkanes. This methodology is environmentally friendly, requires no external additive, and exhibits good functional group compatibility.
Article
Chemistry, Multidisciplinary
Wei Liu, Le Zhang, Ye Liu, Shi-Lu Fan, Jian-Jun Dai, Wei Tao, Hui-Xia Zhu, Hua Xiao
Summary: In this study, a consecutive S(N)2'/S(N)2'' addition of phenol to gamma-vinyl MBH carbonate was performed, leading to the formation of functionalized exocyclohexenes with excellent chemoselectivity. Additionally, using o-hydroxychalcones as pronucleophiles, a series of pharmaceutically intriguing tricyclic chromane derivatives were selectively synthesized through an S(N)2'/S(N)2''/intramolecular Diels-Alder reaction sequence with good diastereoselectivity.
CHEMICAL COMMUNICATIONS
(2022)
