Article
Chemistry, Physical
Miquel Navarro, Macarena G. Alferez, Morgane de Sousa, Juan Miranda-Pizarro, Jesus Campos
Summary: A series of gold(I)-ethylene pi-complexes containing bulky phosphine ligands have been synthesized, and the importance of these ligands in stabilizing the gold(I)-ethylene bond and preventing decomposition has been discovered. By improving the catalyst structure and reaction conditions, the catalytic performance in the hydroamination of ethylene can be enhanced.
Article
Chemistry, Multidisciplinary
Meredith A. Allen, Huy M. Ly, Genevieve F. O'Keefe, Andre M. Beauchemin
Summary: In this study, we report an efficient method for intramolecular hydroamination using a redox-enabled strategy. The process is catalyst-free, mild conditions, and highly functional group tolerant.
Article
Chemistry, Multidisciplinary
Mandapati Bhargava Reddy, Sakthivel Prabhu, Ramasamy Anandhan
Summary: An unprecedented reductive hydroamidative/hydroquinazolinative cascade cyclization of o-alkynylated derivatives was achieved via proton-coupled electron transfer (PCET) under electrolysis. In a single step, the rapid assembly of isoindolinones and novel isoindole-fused quinazolinones were achieved through electrolysis by the hydroamidation of amidyl/quinazolinone aminyl radicals with C-C triple bond addition via 5-exo-dig cyclization followed by olefinic reduction without external reductants. Control and cyclic voltammetry experiments support a mechanistic explanation of the electrochemical cascade, and these experiments indicate that the electrolyte is the source of hydrogen for the olefin reduction.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Xiang Lyu, Changhyeon Seo, Hoimin Jung, Teresa Faber, Dongwook Kim, Sangwon Seo, Sukbok Chang
Summary: Synthetic methods for constructing enantioenriched beta-lactams are highly valuable and challenging due to the formation of strained four-membered rings. This study presents a NiH-catalysed strategy using alkenyl dioxazolone derivatives to overcome the regioselectivity issue. The reaction demonstrates excellent regioselectivity regardless of the electronic properties of substituents and offers a convenient access to enantioenriched beta-lactams.
Article
Chemistry, Multidisciplinary
Yuta Ishikawa, Tatsuya Kameyama, Tsukasa Torimoto, Hajime Maeda, Masahito Segi, Taniyuki Furuyama
Summary: Phthalocyanine ruthenium complexes have been identified as red-light activatable catalysts for trifluoromethylation reactions, enabling the chlorotrifluoromethylation of alkenes without sacrificial reducing reagents. This reaction shows good compatibility with a blue-light-absorbing substrate, unlike traditional photoreaction conditions where the substrate decomposes completely under blue light irradiation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Md. Mahbubur Rahman, Pengcheng Gao, Qun Zhao, Roger Lalancette, Roman Szostak, Michal Szostak
Summary: Cationic Au(i)-NHC complexes have emerged as important catalysts for alkyne & pi;-activation reactions in organic synthesis due to their high stability and reactivity. We report the synthesis and characterization of [Au(NHC)Cl] complexes featuring a new [Au(Np-#)Cl] catalyst, which exhibits higher reactivity and broad applicability. This catalyst has been successfully used in the direct late-stage derivatization of complex pharmaceuticals.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Review
Chemistry, Multidisciplinary
Jorge Escorihuela, Agusti Lledos, Gregori Ujaque
Summary: Hydroamination, the addition of an N-H bond across a C-C multiple bond, is a reaction with significant synthetic potential. This review focuses on achieving anti-Markovnikov regioselectivity in intermolecular hydroaminations of terminal alkynes and alkenes. The mechanisms and factors that favor anti-Markovnikov regioselectivity are discussed, along with alternative pathways and different catalysts.
Article
Chemistry, Organic
Yun-Xing Ji, Jinxia Li, Chun-Min Li, Shuanglin Qu, Bo Zhang
Summary: This study presents a visible-light-promoted method for generating amidyl radicals from N-fluorosulfonamides via a manganese-catalyzed N-F bond activation strategy, using a simple manganese complex and a cheap silane as reactants. This method enables the intramolecular/intermolecular hydroaminations of alkenes, two-component carboamination of alkenes, and even three-component carboamination of alkenes, allowing for the preparation of a wide range of valuable aliphatic sulfonamides.
Review
Chemistry, Multidisciplinary
Ian A. Tonks
Summary: This study discusses the recent progress in Ti-catalyzed oxidative amination reactions, highlighting the importance of understanding the reactive species and mechanisms involved. The research shows that low-valent Ti intermediates can be stabilized through coordination and that reductive elimination processes occur through pi-type electrocyclic reactions. These findings are crucial for advancing catalytic applications involving titanium.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Organic
Yetkin Gok, Beyhan Yigit, Ozlem Ozeroglu Celikal, Murat Yigit
Summary: A series of new rhodium(I) complexes with benzimidazole based N-heterocyclic carbene (NHC) ligand were synthesized and tested as catalysts in the intermolecular hydroamination reactions between styrene with aromatic amines in ionic liquid, showing catalytic activity and selective anti-Markovnikov addition products.
Article
Chemistry, Multidisciplinary
Daven Foster, Pengchao Gao, Ziyun Zhang, Gellert Sipos, Alexandre N. Sobolev, Gareth Nealon, Laura Falivene, Luigi Cavallo, Reto Dorta
Summary: Chiral, cationic NHC-iridium complexes have been introduced as catalysts for the intramolecular hydroamination reaction of unactivated aminoalkenes, showing high activity and selectivity. By eliminating a major deactivation pathway, the efficiency of the reaction is improved. Through experimental and computational studies, valuable insights into the reaction mechanism have been gained.
Article
Chemistry, Multidisciplinary
Robin Cauwenbergh, Prakash Kumar Sahoo, Rakesh Maiti, Abra Mathew, Rositha Kuniyil, Shoubhik Das
Summary: Primary aliphatic amines are important compounds, and finding new chemical routes for their synthesis has gained significant interest. The hydroaminoalkylation reaction is desirable due to the availability and lower price of olefins. The decarboxylative radical-polar crossover process can be used to synthesize functionalized linear aliphatic primary amines.
Article
Chemistry, Organic
Vikram Singh, Bal Krishna Mishra, Deepak Kumar, Bhoopendra Tiwari
Summary: In this study, we have demonstrated a novel method for the construction of C4-heterofunctionalized pyrazolines by introducing heteroatoms onto the ring. This method has important applications for the synthesis of oxyacylated and aminated products with multiple stereocenters.
Article
Chemistry, Organic
Lauriane C. Peyrical, Marie-Rose Ouellet-Du Berger, Maxim Boucher, Melodie Birepinte, Jean-Francois Paquin, Andre B. Charette
Summary: Trifluoromethyl (CF3) and pentafluorosulfanyl (SF5) substituted cyclopropane-fused gamma-lactones were successfully synthesized through Rh2(esp)2-catalyzed intramolecular cyclopropanation, with yields up to 99%. Twelve examples of this interesting scaffold are reported, along with postfunctionalizations to access highly functionalized CF3- and SF5- substituted cyclopropanes. These novel SF5-substituted analogues join the limited list of available pentafluorosulfanyl intermediates.
Article
Chemistry, Multidisciplinary
Christopher M. Brown, David J. Lundberg, Jessica R. Lamb, Ilia Kevlishvili, Denise Kleinschmidt, Yasmeen S. Alfaraj, Heather J. Kulik, Maria Francesca Ottaviani, Nathan J. Oldenhuis, Jeremiah A. Johnson
Summary: This study introduces a modular heterogeneous catalysis platform that immobilizes catalysts onto supports to improve recyclability and efficiency. The approach utilizes self-assembled metal-organic cages/polyhedra to create well-defined catalyst-functionalized junctions, resulting in nanoconfined catalyst domains.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)