Article
Chemistry, Physical
Qing Wang, Kang-Bao Zhong, Hao Xu, Shi-Nan Li, Wei-Ke Zhu, Fei Ye, Zheng Xu, Yu Lan, Li-Wen Xu
Summary: Transition-metal-catalyzed silicon-carbon bond activation is an important process in organosilicon chemistry and homogeneous catalysis. This study reports a convenient and enantioselective Si-C bond cleavage-initiated [4 + 2] annulation, providing access to chiral six-membered oxasilacycles and their derivatives with high yields and enantioselectivities.
Article
Chemistry, Organic
Claire Empel, Thanh Vinh Nguyen, Rene M. Koenigs
Summary: In this study, a nonbenzenoid aromatic carbocation, tropylium, was utilized as an organic Lewis acid catalyst in O-H functionalization reactions of diazoalkanes with benzoic acids, showing excellent efficiency across a wide range of substrates.
Article
Chemistry, Multidisciplinary
Jingfeng Huo, Kangbao Zhong, Yazhen Xue, MyeeMay Lyu, Yifan Ping, Zhenxing Liu, Yu Lan, Jianbo Wang
Summary: This study presents a highly efficient palladium-catalyzed reaction for carbene insertion into strained Si-C bonds, resulting in the asymmetric formation of silacyclopentanes with substituted stereocenters. Mechanistic studies suggest a catalytic cycle involving oxidative addition, carbene migratory insertion, and reductive elimination, as well as the role of chiral ligands in controlling enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Xinzhi Zhang, Yangyang Zhang, Cuijian Liang, Jun Jiang
Summary: This study demonstrated a copper-catalyzed P-H insertion reaction between sulfoxonium ylides and H-phosphorus oxides, yielding alpha-phosphonyl carboxylate derivatives in moderate to high yields. The use of stable sulfoxonium ylides as carbene precursors, along with inexpensive copper catalyst, allows for mild reaction conditions, good functional group compatibility, and easy scale-up, making it attractive for large-scale chemical processing and industrial production.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Veronika Kottisch, Janis Jermaks, Joe-Yee Mak, Ryan A. Woltornist, Tristan H. Lambert, Brett P. Fors
Summary: The novel hydrogen bond donor-organic acid pair facilitates controlled cationic polymerization of vinyl ethers at ambient conditions, allowing for rapid synthesis of high-molecular-weight poly(vinyl ethers).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Mikkel B. Buendia, Bradley Higginson, Soren Kegnaes, Soren Kramer, Ruben Martin
Summary: This article describes a light-induced redox-neutral Ni-catalyzed method for sp3C-H alkylation of unactivated alkenes with alkyl bromides possessing beta-hydrogens. The method stands out for its simplicity, wide applicability, and exquisite regio- and chemoselectivity, providing an entry point to forge sp3-sp3 architectures.
Article
Chemistry, Organic
Chikkabagilu Nagaraju Shambhavi, Masilamani Jeganmohan
Summary: A Ru(II)-catalyzed weak chelating group-aided ortho-C-H alkylation of arylamides with unactivated olefins in a redox-neutral fashion was demonstrated. This reaction was suitable for various substituted arylamides and unactivated aliphatic alkenes, with pivalic acid playing a dual role.
Article
Chemistry, Multidisciplinary
Sofia Strekalova, Alexander Kononov, Ildar Rizvanov, Yulia Budnikova
Summary: A mild and efficient electrochemical method has been developed for the site-selective direct C-H amidation of benzene and its derivatives with acetonitrile and benzonitrile, with up to 78% yield. The process operates under mild conditions (room temperature, ambient pressure, no strong oxidants) that meet the criteria of green chemistry.
Article
Chemistry, Physical
Xiaohu Zhou, Ende Huang, Licheng Zhong, Siyue Liu, Shuze Ma, Hongwei Li, Xueming Yang, Wenrui Dong
Summary: Hydrogen bonding interactions play a crucial role in stabilizing molecular conformations. In this study, the molecular structure of neutral and cationic 2-methoxyethanol (2-ME) was investigated using infrared spectroscopy. The results revealed that neutral 2-ME exhibits a weak O-H…O intramolecular hydrogen bond, while cationic 2-ME lacks this interaction but contains a C-H…O intramolecular hydrogen bond. The comparison between experimental and theoretical spectra identified the most stable conformers and showed that the C-H stretching mode of cationic 2-ME is blue-shifted compared to that of neutral 2-ME. Natural bond orbital analysis provided insights into the weakening of C-H bonds in neutral 2-ME.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Multidisciplinary
Wen-Xuan Cao, Lei Zhu, Yiyi He, Run Wang, Ming Liu, Qin Ouyang, Qing Xiao
Summary: The first aryne insertions into the carbon-iodine bond of heteroaryl iodides have been achieved. This novel reaction provides an efficient pathway for the synthesis of valuable building blocks 2-iodoheterobiaryls with excellent regioselectivity by reacting heteroaryl iodides and o-silylaryl triflates. The copper(I) catalyst, which contains a N-heterocyclic carbene (NHC) ligand, is essential for the reaction. Control reactions and DFT calculations suggest that the coordination of copper, acting as a Lewis acid, with nitrogen atoms of heteroaryl iodides mediates the aryne insertions into heteroaryl carbon-iodine bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Peil, Alejandro Gutierrez Gonzalez, Markus Leutzsch, Alois Fuerstner
Summary: This study demonstrates the highly unorthodox hydrogenation transformation of an internal alkyne using [Cp*RuCl](4) as a precatalyst. The reaction shows regioselectivity and forms vinyl carbene complexes with various binding modes as intermediates. The access to spirocyclic and bridged ring systems through this reaction is of great significance in medicinal chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Ming Hou, Zhide Zhang, Xiaojing Lai, Qianshou Zong, Xinpeng Jiang, Meng Guan, Rui Qi, Guanyinsheng Qiu
Summary: This work reports the efficient application of N-acyloxybenzamides as acyl nitrene precursors under photoredox/iron dual catalysis. The resulting acyl nitrenes can react with various types of C-H bonds and molecules containing S or P atoms. Mechanistic investigations reveal the process of acyl nitrene formation from N-acyloxybenzamides.
Article
Chemistry, Physical
Xuchao Wang, Feipeng Liu, Zijuan Yan, Qing Qiang, Wei Huang, Zi-Qiang Rong
Summary: The study introduces a redox-neutral Ni-catalyzed cross-coupling reaction that converts two readily available precursors into ketones, which are important structural motifs in various biologically active compounds. By using a commercially available nickel/Triphos catalytic system, a wide range of easily accessible alkenyl primary alcohols and aryltriflates can be efficiently converted into ketones with good yields and functional group tolerance. This transformation also demonstrates its utility in late-stage functionalization of a large set of complex molecules to access more functionalized aromatic ketones.
Article
Chemistry, Organic
Zhenbang Chen, Zengming Shen
Summary: An efficient method for Ni-catalyzed asymmetric reductive arylcyanation of alkenes is developed, producing chiral 3-cyanomethyl oxindoles with all-carbon quaternary stereocenters in high yields and enantioselectivities. The use of acetonitrile as a cyano source through beta-carbon elimination assisted by Zn(OTf)(2) avoids the release of free cyanide anions, preventing competitive coordination with the metal center and maintaining enantioselectivity. This method also finds valuable applications in the synthesis of natural alkaloids (-)-physostigmine and (-)-esermethole.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Gilles De Smet, Xingfeng Bai, Carl Mensch, Sergey Sergeyev, Gwilherm Evano, Bert U. W. Maes
Summary: This study demonstrates that acetate can serve as a renewable leaving group for selective deoxygenation of phenolics. The Ni-catalyzed reaction in a green solvent allows for efficient deoxygenation without affecting specific functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)