Article
Chemistry, Organic
Kosuke Kato, Kazutada Ikeuchi, Takahiro Suzuki, Keiji Tanino
Summary: A new method for constructing the bicyclo[3.2.1]octane skeleton was developed using intramolecular alkylation. The total synthesis of 2-isocyanoallopupukeanane was achieved via a 17-step transformation, showcasing the significance of this synthetic method in constructing complex organic molecules.
Article
Chemistry, Organic
Jun Li, Zhi-Wen Zhao, Shuang Zheng, Ping He, Ji-Ying Qiu, Quan-Quan Zhou, Zhi-Lin Ren
Summary: Herein, we describe a novel one-pot method for the synthesis of polysubstituted pyrrole derivatives via a three-component reaction of alkenyl bromides, amines, and isocyanides. The conversion process is catalyzed by a Pd catalyst without the need for additional ligands. The key feature of this method is the orderly insertion of three isocyanide molecules, directed by the intramolecular imine group. Additionally, DFT calculations provide support for the proposed reaction mechanism.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Applied
Jesus Albarran-Velo, Vicente Gotor-Fernandez, Ivan Lavandera
Summary: The study presents a photo-metal-catalyzed oxidation reaction to efficiently synthesize methyl ketones. By utilizing a palladium complex and a photosensitizer, along with blue LED light irradiation in aqueous medium at room temperature, the desired carbonyl compounds were obtained with high conversions and excellent selectivities.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Shu-Hui Lei, Ya Zhong, Xian-Peng Cai, Qing Huang, Jian-Ping Qu, Yan-Biao Kang
Summary: A tandem isomerization-anti-Markovnikov oxidation method has been developed using bis(benzonitrile)palladium chloride catalyst and O-2 as the sole oxidant, regiospecifically yielding beta-amino aldehydes. tert-Butyl nitrite serves as a simple and only redox cocatalyst, with (BuOH)-Bu-t as a crucial solvent for achieving excellent yield and specificity toward anti-Markovnikov aldehyde products.
Article
Chemistry, Organic
Shu-Hui Lei, Ya Zhong, Xian-Peng Cai, Qing Huang, Jian-Ping Qu, Yan-Biao Kang
Summary: A simple and practical method for the preparation of beta-O substituted aldehydes directly from linear allylic esters has been developed. By using a specific catalyst and oxidant, the reaction proceeds smoothly to give the desired products, showing broad substrate scope and excellent regioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Dianpeng Chen, Jianming Li, Xiuhua Zhang, Gongle Liu, Xin Wang, Yongwei Liu, Xuan Liu, Yingying Shan
Summary: A novel method for the synthesis of fused tetracyclic N-heterocycles is described using palladium-catalyzed cyclization of isocyanides with alkyne-tethered aryl iodides. The reaction involves a unique amino-to-alkyl 1,5-palladium migration/intramolecular C(sp(3))-C(sp(2)) coupling sequence. Isocyanide plays multiple roles in this transformation, serving as a C1 synthon, a C1N1 synthon, and the donor of C(sp(3)) for C(sp(3))-C(sp(2)) coupling, and it represents the only successful example of C(sp(3))-H activation of isocyanide.
Article
Chemistry, Organic
Rodney A. Fernandes, Sandhya S. Yadav, Praveen Kumar
Summary: This paper presents an efficient palladium-catalyzed anti-Markovnikov oxidative acetalization of activated terminal olefins with iron(iii) sulfate as the reoxidant, under mild reaction conditions. The methodology exhibits high regioselectivity towards anti-Markovnikov products and compatibility with a wide range of functional groups. Iron(iii) sulfate is the sole reoxidant used, providing various anti-Markovnikov acetals, including orthogonally functionalized 1,3- and 1,4-dioxygenated compounds.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Physical
Jerick Imbao, Jeroen A. van Bokhoven, Maarten Nachtegaal
Summary: The kinetic studies and X-ray absorption spectroscopy revealed the role of water in the Wacker-type ethylene oxidation, showing that water plays a key role in the reoxidation of Pd and Cu, aiding in more efficient electron transfer.
Article
Chemistry, Multidisciplinary
Yasuyuki Ura
Summary: This paper describes the challenging realization of anti-Markovnikov selectivity in Pd-catalyzed reactions, with key factors including the steric bulkiness of oxygen nucleophiles and electron-deficient cyclic alkenes as additives.
Article
Chemistry, Multidisciplinary
Toru Hashimoto, Tsubasa Maruyama, Toshiya Ishimaru, Masaru Matsugaki, Keisuke Shiota, Yoshitaka Yamaguchi
Summary: A Wacker-Tsuji-Type oxidation reaction using molecular oxygen and TMDS catalyzed by ferrate has been developed for the oxidation of styrene derivatives to ketones, with good yields. The system can also achieve cleavage of the C-C double bond of alpha-phenyl-substituted styrene derivatives to provide one-carbon-degraded ketones in good yield.
Article
Chemistry, Applied
Shubhangi P. Bhoite, Gurunath Suryavanshi
Summary: A simple synthetic approach has been developed to efficiently synthesize related compounds using commercially available starting materials through allylation, oxidation, and reduction reactions.
NATURAL PRODUCT RESEARCH
(2023)
Article
Chemistry, Physical
Jonathan Trouve, Khalil Youssef, Sitthichok Kasemthaveechok, Rafael Gramage-Doria
Summary: Iron catalysts enable Markovnikov-selective reactions, achieving up to 99% selectivity for ketone products from (hetero)aromatic and aliphatic olefins under ambient conditions. The catalyst design, inspired by the promiscuous activity of cytochromes P-450 enzymes, allows the formation of iron-hydride species under catalytically relevant conditions, leading to the desired selectivity.
Review
Chemistry, Organic
Jacques Muzart
Summary: The Wacker-type reactions of terminal alkenes generally result in the formation of methyl ketones instead of aldehydes, requiring specific coordinating fragments for selective aldehyde formation. However, a few methods have been found to provide fair to high aldehyde/methyl ketone ratios even in the absence of directing groups. This review focuses on the formation of aldehydes and summarizes the reported methods since 2007, along with proposed mechanisms and intermediates to rationalize regioselectivity.
Article
Chemistry, Multidisciplinary
Yang Ye, Jiandong Liu, Bing Xu, Songwei Jiang, Renren Bai, Shijun Li, Tian Xie, Xiang-Yang Ye
Summary: A novel nickel-catalyzed asymmetric 1,2-vinylboration reaction has been developed for the efficient preparation of chiral compounds with high yields and excellent enantioselectivities. The method shows exceptional chemo- and stereoselectivity and has potential applications in the asymmetric modification of structurally complex natural products and pharmaceuticals.
Article
Chemistry, Multidisciplinary
Yuchan Han, Li Wu, Qi Han, Rongfan Zhang, Jun Li
Summary: Novel palladium-based catalysts were synthesized by attaching Pd(OAc)(2) to surface-modified mesoporous silica and graphene oxide. The physical and chemical properties of the catalysts were characterized. The stability of the catalyst and the heterogeneity of the reaction system were investigated through different approaches, and the performance of the catalyst SBA-15-B-Pd was found to be superior to that of GO-B-Pd. The catalysts could be reused multiple times without significant loss of performance.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Alexander Reichle, Hannes Sterzel, Peter Kreitmeier, Remi Fayad, Felix N. Castellano, Julia Rehbein, Oliver Reiser
Summary: The study showcases the concept of light-induced homolysis for radical generation in Cu-II-photocatalyzed decarboxylative oxygenation. Two Cu-II-carboxylate complexes with different coordination geometries were synthesized and characterized by X-ray analysis, correlating their structure with their ability to initiate light-induced decarboxylations.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Quan-Qing Zhao, Julia Rehbein, Oliver Reiser
Summary: This study presents a visible-light-driven dearomatization reaction of unactivated arenes, enabling efficient synthesis of spiro-1,4-cyclohexadienes. Calculations indicate that the overall process is thermoneutral, highlighting the potential of light-driven processes in developing sustainable transformations that defy thermodynamic requirements.
Article
Chemistry, Organic
Tobias Babl, Oliver Reiser
Summary: The first enantioselective synthesis of (S)-meptazinol in 14 steps from a commercially available compound and the formal synthesis of two anti-Alzheimer's agents are reported. A novel ring expansion reaction provides an effective entry to 3,3-disubstituted azepanes that represent the core for a variety of approved drugs.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Manoj Kumar, Shalini Verma, Vivek Mishra, Oliver Reiser, Akhilesh K. Verma
Summary: The copper-catalyzed reactions under visible light irradiation have been successfully applied in the synthesis of aminated cyclopentene and cyclopentane derivatives. The method is compatible with various functionalities and demonstrates simplicity and affordability.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Woraluk Mansawat, Phanomsak Yukhet, Worawan Bhanthumnavin, Oliver Reiser, Tirayut Vilaivan
Summary: The use of C-2-symmetrical chiral amino alcohol ligands in combination with CuCl2 has been shown to be effective for the asymmetric acylation of dI-hydrobenzoins, with up to 99% ee obtained for the monoacylated products.
Article
Chemistry, Multidisciplinary
Alexander Reichle, Magdalena Koch, Hannes Sterzel, Lea-Joy Grosskopf, Johannes Floss, Julia Rehbein, Oliver Reiser
Summary: The visible light-mediated copper-catalyzed vicinal difunctionalization of olefins utilizing bromonitroalkanes as ATRA reagents is reported. This method offers high yields, fast reaction times, and environmentally benign reaction conditions with a wide scope, allowing rapid functionalization of activated and unactivated olefins. Additionally, it demonstrates the late-stage functionalization of biologically active molecules and the upscaling to gram quantities, providing possibilities for further transformations such as the preparation of nitro- and aminocyclopropanes. Moreover, this study highlights the unique role of copper in photoredox catalysis by stabilizing and interacting with radical intermediates in its coordination sphere, as revealed by EPR studies that show its superior performance compared to iridium-based photocatalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Nejc Petek, Helena Brodnik, Oliver Reiser, Bogdan Stefane
Summary: A Cu(I)-photoredox-catalyzed trifluoromethylchlorosulfonylation reaction of terminal alkynes under visible light conditions has been developed. The reaction yields trifluoromethyl-substituted vinylsulfonyl chlorides, which can subsequently be coupled to a second alkyne under photocatalytic conditions. The method shows high regio- and stereoselectivity and can be applied to aliphatic and aromatic alkynes with various functional groups, producing synthetically valuable intermediates.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sebastian Fischer, Terrence-Thang H. Nguyen, Andreas Ratzenboeck, Huw M. L. Davies, Oliver Reiser
Summary: A stereoselective, solvent- and metal-free method for endocyclic C-C bond cleavage of monocyclopropanated cyclopentadienes mediated by strong acids has been developed. It leads to the formation of highly functionalized six-membered carbocycles with high stereocontrol. The critical step involves the formation of a cyclopropyl carbocation that undergoes endocyclic ring opening through an SN2'-type attack of various nucleophiles. Subsequent synthetic transformations demonstrate the versatility of the resulting cyclohexenes for the synthesis of compounds with nonconventional substitution patterns.
Article
Chemistry, Organic
Daniel Dobler, Michael Leitner, Peter Kreitmeier, Oliver Reiser
Summary: An atom-efficient method for synthesizing 2-pyrone on a multigram scale was developed using a large-scale thermal rearrangement of cyclopentadienone epoxide as the key step. This approach also provides easy access to 6-substituted 2-pyrone natural product derivatives.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Sujittra Paenkaew, Usana Mahanitipong, Metha Rutnakornpituk, Oliver Reiser
Summary: A thermoresponsive and recyclable nanomaterial was synthesized by modifying magnetite nanoparticles (MNPs) with poly(N-isopropylacrylamide-co-diethylaminoethyl methacrylate) (P(NIPAAm-co-DEAEMA)), which contained thermoresponsive PNIPAAm and catalyst binding PDEAEMA. Pd nanoparticles were incorporated into this material, creating a nanocatalyst that exhibited high catalytic activity for the hydrogenation of olefins and nitro compounds with turnover frequencies (TOFs) up to 750 h-1. The catalyst maintained consistent catalytic activity over 10 consecutive runs by performing the hydrogenation above the lower critical solution temperature (LCST) of the copolymer (37 degrees C) and then cooling below the LCST (15 degrees C).
Article
Chemistry, Multidisciplinary
Tirtha Mandal, Narenderreddy Katta, Hendrik Paps, Oliver Reiser
Summary: This paper presents a sequential photocatalytic strategy that combines Cu(II)/Cu(I)-catalytic cycles for the oxoallylation of vinyl arenes using a-haloketones. Initially, Cu(II)-photocatalyzed oxohalogenation generates halide radicals from acyl halides, utilizing air as an oxidant, and can be used for late-stage modification of pharmaceuticals and agrochemicals. The subsequent one-pot Cu(I)-photocatalyzed allylation of a-bromoketones proceeds with high regio- and chemoselectivity, unaffected by the electronic nature of the styrenes.
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Multidisciplinary
Alexander Reichle, Oliver Reiser
Summary: Photocatalysis has become a powerful strategy for selective functionalization of molecules through radical intermediates. While iridium or ruthenium-based photocatalysts have been well-studied, the use of earth-abundant metal-based photocatalysts is less explored. Recently, the concept of light-induced homolysis using earth-abundant 3d-metal complexes has gained significant interest despite their short excited-state lifetimes. Cu(ii)-complexes play a prominent role in this concept and recent developments in organic synthesis showcase the future prospects of this growing field.
Review
Chemistry, Multidisciplinary
Sebastian Engl, Oliver Reiser
Summary: Atom transfer radical addition (ATRA) reactions are important transformations in synthetic chemistry for the difunctionalization of alkenes using simple starting materials. The recent advancement in photocatalysis, particularly using copper complexes, has provided a mild and energy-efficient alternative to the traditional methods that required toxic initiators or harsh thermal conditions. Copper photocatalysis has the advantage of enabling ligand exchange and facilitating transformations utilizing their coordination sphere. It also allows the access to two-component and three-component ATRA reactions that were not feasible with other catalysts like ruthenium or iridium. This review highlights the emerging field of using Cu(i)-substrate assemblies as active photocatalysts for achieving three-component coupling reactions under enantioselective control.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Pawittra Chaibuth, Nontakarn Chuaytanee, Jutawat Hojitsiriyanont, Kittipong Chainok, Sumrit Wacharasindhu, Oliver Reiser, Mongkol Sukwattanasinitt
Summary: The catalytic properties of copper(II) complexes and their application in atom transfer radical addition (ATRA) reactions of alkyl halides to alkenes were studied. The complexes were effectively reduced to active copper(I) species through Eight-induced homolysis, enabling efficient catalysis of the addition reaction at room temperature. The complexes can be conveniently generated in situ for the reaction and exhibit excellent regio- and stereoselectivity.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Safoora Sheikh, Mohammad Ali Nasseri, Mohammad Chahkandi, Oliver Reiser, Ali Allahresani
Summary: A recyclable nanomagnetic catalyst PAMAM G(0)-Pd@gamma-Fe2O3 is reported for catalytic C-C cross-coupling reactions of challenging substrates. The catalyst exhibits good solubility and catalytic activity for a variety of aryl chloride substrates under mild reaction conditions in aqueous media. The immobilization of the catalyst on a magnetic platform allows for effective recovery and reuse.
