Article
Chemistry, Organic
Ayushee, Monika Patel, Priyanka Meena, Kousar Jahan, Prasad Bharatam, Akhilesh K. Verma
Summary: A base-promoted protocol was investigated for the intermolecular anti-Markovnikov hydroamidation of vinyl arenes, leading to the formation of arylethylbenzamides with excellent chemo- and regioselectivity. The reaction demonstrated high chemoselectivity for the amide group over amine and tolerance towards a wide variety of functional groups. The proposed mechanism and the importance of the solvent were supported by deuterium labeling studies and control experiments.
Article
Chemistry, Organic
Binbin Huang, Guiling Chen, Haoxiang Zhang, Xinye Tang, Jiawei Yuan, Caicai Lu, Junlei Wang
Summary: A mild and simple electrochemical system using potassium iodide as the only additive has been developed for efficient cyclization of 2-ethynylanilines in a non-volatile aqueous solvent. By altering the electrode material and charge passed, selective formation of either 3-iodoindoles or indoles with high efficiency and broad substrate scope was achieved. The synthetic potential of this method was demonstrated through late-stage functionalization, gram-scale synthesis, and further derivatization. Mechanistic studies indicated that cathodic generation of base (HO-) from reduction of water also played a crucial role in these efficient conversions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Jun-Sheng Wei, Song Yang, Yin Wei, Sima Shamsaddinimotlagh, Hossein Tavakol, Min Shi
Summary: A gold(i)-catalyzed intramolecular cyclization reaction was developed to synthesize functionalized morpholines, piperazines, and oxazepanes. The reaction proceeds via a carbene or non-carbene process and exhibits a broad substrate scope, good functional group tolerance, and mild reaction conditions. The reaction pathway can be modulated by the steric bulkiness or chain length of the substrate.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Arnaud Clerc, Enrico Marelli, Nicolas Adet, Julien Monot, Blanca Martin-Vaca, Didier Bourissou
Summary: The new catalytic approach combines metal-ligand cooperation and Lewis acid activation to efficiently react with a variety of complex substrates, providing a new solution for the Conia-ene reaction.
Article
Chemistry, Organic
Shangyuan Wang, Jiajun Zhao, Jun Ying, Xiao-Feng Wu
Summary: This study developed a palladium-catalyzed one-pot two-step radical mediated carbonylative cyclization method to construct polycyclic 3,4-dihydroquinolin-2-(1H)-one scaffolds using perfluoroalkyl iodides and Mo-(CO)(6) with 1,7-enynes. Various polycyclic 3,4-dihydroquinolin-2-(1H)-one derivatives containing perfluoroalkyl and carbonyl units were synthesized with high yields. Moreover, modification of several bioactive molecules was demonstrated using this protocol.
Article
Chemistry, Organic
Kun Hu, Ruiting Liu, Xigeng Zhou
Summary: The rare earth metal-catalyzed reaction allows for the straightforward synthesis of new functional dibenzo[c,e]azepines from 2-nitrile-2'-alkenyl-(alkynyl) biphenyls and amines, avoiding the need for additives and demonstrating high yield and selectivity.
Article
Chemistry, Organic
Hanhan Wang, Mengjun Hu, Xiao-Na Wang, Junbiao Chang
Summary: Efforts for developing a convenient and expeditious method for the synthesis of alkoxy-substituted enamides via nucleophilic addition of alcohols to ynesulfonamides are described in this study. The reaction sequence is shown to be completely regioselective and highly stereoselective, resulting in high yields of hydroalkoxylation products under mild reaction conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Tianmei Zhang, Min Cai, Wenfeng Zhao, Mao Liu, Nan Jiang, Qingmei Ge, Hang Cong
Summary: We developed a practical and efficient electrochemical approach for the synthesis of pi-conjugated phosphonium salts through intramolecular annulation and C-P bond construction. This reaction took place under catalyst- and adscititious oxidant-free conditions at room temperature. A variety of substituted pi-conjugated phosphonium salt products were obtained with good functional group tolerance and yields. A gram-scale reaction demonstrated the potential of this protocol for practical applications. Preliminary mechanistic studies suggested the involvement of free radicals in this process.
Article
Chemistry, Organic
Zhidong Jiang, Jianhui Zhou, Haoran Zhu, Hong Liu, Yu Zhou
Summary: A novel Rh(III)-catalyzed C-H activation/annulation cascade of indole-enaminones with diazo compounds was reported, generating diversely functionalized carbazole frameworks with good to excellent yields. The most notable feature is the formation of a novel [5 + 1] cyclization product, accompanied by the complete removal of acetyl and N,N-dimethyl groups from the substrates, rather than the expected [4 + 2] cyclization products.
Article
Chemistry, Physical
Xian Xu, Xizhou Zheng, Xin Xu
Summary: A redox-neutral C-H/N-H annulation of anilines with allenes and dienes was achieved using a scandium catalyst with a simple beta-diketiminato ligand. The reaction selectively produced a family of tetrahydroquinolines in high isolated yields, with both allene and diene coupling partners serving as three-carbon building blocks. Mechanistic investigations suggested a reaction pathway involving N-H allylation, Hofmann-Martius rearrangement, and hydroamination cyclization.
Article
Chemistry, Physical
Yang Gao, Simin Yang, Yanping Huo, Qian Chen, Xianwei Li, Xiao-Qiang Hu
Summary: A highly efficient NiH catalytic system was developed for the selective hydroamination of alkynes, leading to structurally diverse quinolines. This method is applicable to a wide range of alkynes and has shown utility in the functionalization of natural products and the synthesis of complex molecules. Preliminary mechanistic experiments suggest an alkenylnickel-mediated alkyne hydroamination and intramolecular cyclization of enamine intermediates.
Article
Chemistry, Organic
Yoshihiko Morimoto, Moe Hamada, Shotaro Takano, Katsufumi Mochizuki, Takuya Kochi, Fumitoshi Kakiuchi
Summary: Utilizing 8-quinolinolato rhodium catalysts and CsF, the coupling of alkylacetylenes with secondary amines in both 2:1 and 1:1 ratios was achieved. The solvent choice can switch the selectivity between 2:1 and 1:1 ratios, leading to different products under different reaction conditions.Additionally, anti-Markovnikov hydroamination reactions in toluene resulted in 1:1 coupling products under relatively mild conditions.
Article
Chemistry, Physical
Lu Ouyang, Yuqiu Liang, Sen Wang, Rui Miao, Jianhua Liao, Zhanhui Yang, Renshi Luo
Summary: Here, we report an efficient one-pot iridium-catalyzed reductive hydroamination of terminal alkynes with amines, which allows for the formation of complex aliphatic amines. This transformation not only employs inexpensive and easily accessible HCO2H as the reducing agent, but also utilizes water as the reaction media, aligning with the principles of green and sustainable chemistry.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Jeymy T. Sarmiento, Maria Carcel, Carmen Ramirez de Arellano, Teresa Varea, Gregorio Asensio, Andrea Olmos
Summary: In this study, alpha-chloromethylketimines have been synthesized through a gold-catalyzed hydroamination reaction of aromatic and aliphatic 1-chloroalkynes with aromatic amines. This method allows the preparation and spectroscopic characterization of alpha-chloromethylketimines with high purity, complete conversion, and atom economy. The synthetic usefulness of this methodology has been demonstrated through the preparation of beta-chloroamines and indoles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jeymy T. T. Sarmiento, Maria Carcel, Carmen Ramirez de Arellano, Teresa Varea, Gregorio Asensio, Andrea Olmos
Summary: α-Chloromethylketimines have been synthesized through a gold-catalyzed hydroamination reaction of aromatic amines with aromatic and aliphatic 1-chloroalkynes. This method allows for the preparation and spectroscopic characterization of α-chloromethylketimines, as well as the synthesis of β-chloroamines and indoles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)