Article
Chemistry, Organic
Sabrina Giofre, Camilla Loro, Letizia Molteni, Carlo Castellano, Alessandro Contini, Donatella Nava, Gianluigi Broggini, Egle M. Beccalli
Summary: A useful aminohalogenation reaction for the cyclization of O-alkynyl carbamates under copper catalysis has been developed in this study. N-Halosuccinimides were used as the halogen source, leading to selective intramolecular C-N bond formation and the generation of haloalkylidene substituted heterocycles. The mechanism for the two alternative reaction pathways was investigated by modeling the corresponding transition states at the DFT level.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ju Eun Jeon, Siyeon Jeong, Hayeon Kwak, Jung Min Joo
Summary: In this study, gold(III)-catalyzed cyclization reactions of alkynyl norbornene derivatives were developed to generate benzofused (hetero)arenes with substitutions at the benzocyclic ring. The combination of Au(OAc)(3) and AgNTf2 allowed for the annulation of (hetero)arenes by intramolecular hydro(hetero)arylation followed by retroDiels-Alder reactions to afford fully conjugated benzofused (hetero)arenes in higher yields than the previously developed Pd(OAc)(2)-catalyzed protocol. Additionally, using AuCl3 instead of Au(OAc)(3) led to a rearrangement of (hetero)arenes with the norbornene bridge installed at the more electron-rich and sterically demanding position to afford the corresponding regioisomeric products in a divergent manner. These results highlight the importance of steric effects in addition to the electronic effects of the catalyst and the substrate on the rearrangement.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Jackson J. Hernandez, Alison J. Frontier
Summary: We report a Bronsted acid-catalyzed carbocyclization cascade that enables the synthesis of fused heterotricycles. The method exhibits high diastereoselectivity and produces versatile scaffolds with various functional groups for further derivatization.
Review
Chemistry, Applied
Alexey A. Festa, Pavel Raspertov, Leonid G. Voskressensky
Summary: This survey explores the transformations of 2-alkynylanilines and their derivatives into heterocycles. Depending on various factors, such as substituents, catalysts, and reaction conditions, these substrates can form different types of heterocyclic compounds. The survey summarizes the ability of these substrates to produce heterocycles of different ring sizes.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Xinhang Zhang, Hanyang Sun, Changhong Han, He Wang, Junpeng Zhang, Di Zhang, Bin Lin, Huiming Hua, Maosheng Cheng, Yongxiang Liu
Summary: The asymmetric total synthesis of neobraclactone C was achieved for the first time using a convergent synthetic strategy, with the longest linear sequence of 22 steps from known materials. Key steps of the synthesis include a steric hindrance/hydrogen bond dual-controlled Heck arylation reaction for the construction of hemiketal and cis-alkenyl in one step, as well as a CeCl3-catalyzed tricycle formation.
Article
Chemistry, Inorganic & Nuclear
Felipe de la Cruz-Martinez, Marc Martinez de Sarasa Buchaca, Juan Fernandez-Baeza, Luis F. Sanchez-Barba, Ana M. Rodriguez, Jose A. Castro-Osma, Agustin Lara-Sanchez
Summary: Despite the widespread interest in zinc catalysis for hydroelementation reactions, the use of zinc complexes as catalysts for the hydroalkoxylation of alkynyl alcohols has not been reported. However, scorpionate zinc complexes have been successfully designed as precatalysts for this reaction. Studies have shown the excellent selectivity of zinc amide complex 8 in promoting the intramolecular hydroalkoxylation process to yield exocyclic enol ethers under mild conditions.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Shangfeng Ren, Keke Huang, Jin-Biao Liu, Lianpeng Zhang, Min Hou, Guanyinsheng Qiu
Summary: A palladium-catalyzed formal [2 + 2 + 1] cyclization of 1-alkynyl-8-iodonaphthalene with double isocyanides is developed, resulting in a series of 7H-acenaphtho[1,2-b]pyrrole compounds.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Physical
Wen-Bin Xie, Zhi Li
Summary: A series of chiral compounds were designed and synthesized for a highly enantioselective intramolecular hydroalkoxylation of nonactivated alkenes, resulting in the formation of 2-methylcoumarans with up to 99% yields and up to 97% enantiomeric excess under mild conditions.
Article
Chemistry, Multidisciplinary
Bowen Dou, Kang Wang, Jianbo Wang
Summary: In this paper, we report an efficient method for the synthesis of alkynylated furan derivatives using a Pd-catalyzed oxidative cross-coupling reaction between allenyl ketones and terminal alkynes. This novel synthesis demonstrates the generality of carbene-based cross coupling, and offers an operationally simple and wide substrate scope approach to access alkynylated furan derivatives with good functional group tolerance.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Akshay Subhash Narode, Rai-Shung Liu
Summary: Gold(I)-catalyzed reactions between 1-(1-alkynyl) cyclopropyl ketones and vinyldiazo ketones to produce substituted [(furan-3-yl)ethyl]-1H-pyrazol-5-yl)methanones are described. In this reaction sequence, the vinyldiazo ketones undergo a thermal cyclization to produce pyrazole intermediates that attack gold-containing all-carbon 1,4-carbon dipoles, resulting in the formation of the observed products. The atypical N(1)-regioselectivity in this reaction model is also explained.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zhiqiong Tang, Fang Zhang, Tengfei Yao, Xun-Shen Liu, Yuanyuan Liu, Lu Liu
Summary: This paper presents a dearomative iodocyclization of N-(o-alkynyl)aryl isoindole, which leads to the formation of various biologically active benzoindoleazine skeletons containing alkenyl iodine. The resulting products can undergo further cycloaddition or coupling reactions to form a series of highly functionalized N-fused polycyclic scaffolds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Carl T. Bormann, Christeena Mathew, Margarida M. Antonio, Aude Trotti, Farzaneh Fadaei-Tirani, Kay Severin
Summary: In this study, the synthesis of a terminal 1-alkynyl triazene is described, and subsequent functionalization expands the structural diversity of this compound class. Furthermore, its applications in the synthesis of di- and triynes, as well as in the preparation of (hetero)aromatic triazenes through metal-catalyzed cyclization reactions, are explored.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xin-Yang Fan, Jia-Cheng Li, Ji-Jia Zhou, Bo Zhou, Long-Wu Ye
Summary: A new chiral Bronsted acid-catalyzed reaction has been developed for the asymmetric spirocyclization of alkynyl thioethers via dearomatization of phenols. This metal-free method enables the efficient and stereocontrolled synthesis of chiral spiro[4.5]decan-6-ones, with high yields and enantioselectivities. It provides a green and atom-economical approach for the preparation of these compounds.
Review
Chemistry, Multidisciplinary
Abdusalom A. Suleymanov, Kay Severin
Summary: Recent developments have revealed that vinyl and alkynyl triazenes are highly interesting compounds with unique reactivity, enabled by the electron-donating properties of the triazenyl group. These compounds can be prepared in few steps from readily available starting materials, making them a promising area of study in synthetic organic and medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jin-Fay Tan, Carl Thomas Bormann, Kay Severin, Nicolai Cramer
Summary: The 2-pyrone motif in bioactive natural products can be modified through the properties of 1-alkynyl triazenes with the addition of propiolic acids and subsequent cyclization induced by silver salt. Different triazenyl derivatives of 2-pyrones can be selectively formed depending on reaction temperature and further replaced by various groups, leading to valuable compounds such as 2-fluoro pyrones. The triazenyl group also plays a role in subsequent Diels-Alder cycloadditions and in the formation of rare fused aminopyrazole pyrone heterocycles.
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin, Emma Richards
Summary: Ionic compounds containing sodium cations are known for their stability and resistance to redox reactivity. However, when treated with non-reducible organic bases, a low oxidation state {Mg2Na2} species undergoes selective extrusion of sodium metal and oxidation of the Mg-I centers. Quantum chemical studies indicate that intramolecular electron transfer is facilitated by the molecular orbitals of the {Mg2Na2} ensemble.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Laura E. English, Thomas M. Horsley Downie, Catherine L. Lyall, Mary F. Mahon, Claire L. McMullin, Samuel E. Neale, Carla M. Saunders, David J. Liptrot
Summary: The (IPr)CuOtBu catalysed reduction of 11 aryl and alkyl isocyanates with pinacolborane resulted in the formation of boraformamides, pinBN(R)C(O)H, in most cases. Overreduction was observed only for electron poor aryl isocyanates (4-NC-C6H4NCO, 4-F3C-C6H4NCO, 3-O2N-C6H4NCO). Computational analysis revealed that the stability of [(IPr)CuH](2), proposed as the catalyst resting state, influences selectivity and offers a potential solution to prevent overreduction in future work. In the case of iPrNCO, the formation of [(IPr)CuH](2) prevents overreduction kinetically. However, for 4-NC-C6H4NCO, the barrier height for the first step of overreduction is much lower, resulting in unselective reduction.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Kyle G. G. Pearce, Michael S. S. Hill, Mary F. F. Mahon
Summary: Reaction of BeCl2 with dilithium diamide yields the dimeric chloroberyllate, leading to the formation of a 2-coordinate beryllium amide. Reduction of the beryllium amide using lithium or sodium in benzene produces relevant organoberyllate products, likely through transient Be(i) radicals.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Henry T. W. Shere, Michael S. Hill, Samuel E. Neale, Mary F. Mahon, Claire L. McMullin, Andrew S. S. Wilson
Summary: This article investigates the contrasting reactivities of molecular beta-diketiminato (BDI) calcium hydride and n-hexyl derivatives towards bis(pinacolato)diboron (B(2)pin(2)). The study finds that the dimeric calcium hydride forms an unusual diborane(6) dianion, while the initially dimeric organocalcium reagent converts to a calcium diboranate monomer. Attempts to induce heterolysis of the B-B bond in the calcium diboranate monomer were unsuccessful, resulting in either dismutation or the generation of N-donor adduct derivatives. These different reactivities can be explained by density functional theory (DFT) calculations, which attribute them to the larger radius and lower steric congestion of the third-row group 2 cation.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2023)
Article
Chemistry, Inorganic & Nuclear
Anne-Frederique M. Pecharman, Erika M. Roberts, Fedor M. Miloserdov, Victor Varela-Izquierdo, Mary F. Mahon, Michael K. Whittlesey
Summary: The addition of excess ZnMe2 to a mixture of [Ru(PPh3)(3)HCl] and IMes resulted in the formation of a bis-cyclometallated complex [Ru(IMes)(PPh3)(2)] 2 and a mono-cyclometallated Ru-Zn heterobimetallic complex [Ru(IMes)'(PPh3)(2)(ZnMe)] 3. Further reactions of these complexes with H-2, PhSiH3, pinacolborane, and CO were investigated. Compounds 1, 4, 5, and 6 were synthesized and structurally characterized.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Han-Ying Liu, Mary F. Mahon, Michael S. Hill
Summary: The potassium diamidoalumanyl reacts with pinacolato boron esters and B(OMe) to produce potassium (alkoxy)borylaluminate derivatives. The reactivity of these derivatives with heteroallene molecules highlights the kinetic inaccessibility of their Al-B bonds.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Anne-Frederique M. Pecharman, Rosalyn L. Falconer, Esme Owen, Michael J. Cowley, John P. Lowe, Claire L. McMullin, Mary F. Mahon, Michael K. Whittlesey
Summary: Treatment of [Ru(L)(PPh3)2(CO)H2] (L = PPh3, IMes) with an N-mesityl amidophosphine aluminium dihydride complex (Al(P-N)H2) gives [Ru(PPh3)2(CO)H3{Al(P-N)H}] (2) and [Ru(IMes)(PPh3)(CO)H3{Al(P-N)H}] (4), which are present in solution as mixtures of diastereomers. Crystal structure determinations and density functional theory (DFT) calculations suggest both 2 and 4 can be formulated as [Ru(L)(PPh3)(CO)H3][Al(P-N)H] complexes with bridging hydride ligands.
Article
Chemistry, Inorganic & Nuclear
Henry T. W. Shere, Michael S. Hill, Mary F. Mahon
Summary: This contribution describes the formation of homonuclear sigma bonding between boron mediated by alkaline earth metals. The reaction between alkaline earth bis-(trimethylsilyl)amides and bis(pinacolato)diboron resulted in the formation of group 2 silazide diborane adducts. Further reaction with bis(pinacolato)diboron led to the formation of bis-triboranate derivatives. These complexes provide rare examples of catena-boron species with propagated B-B bonds beyond the common diboranes.
Article
Chemistry, Multidisciplinary
Kyle G. Pearce, Chiara Dinoi, Ryan J. Schwamm, Laurent Maron, Mary F. Mahon, Michael S. Hill
Summary: This study investigates the formation of a series of calcium complexes, in which the orientation and hapticity of the aryl units are influenced by the position of the methyl substituent and steric hindrance. Additionally, an unusual reaction mechanism involving the generation of an intermediate dicalcium species and the polyhapto engagement of the aryl substituents with calcium is observed.
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin, Benjamin L. Morrison
Summary: [{SiNDipp}MgNa](2) reacts directly with H-2 to form a heterobimetallic hydride. Computational density functional theory (DFT) studies suggest that this reactivity is initiated by orbitally-constrained sigma(Mg-Mg)-> sigma*(H-H) and sigma(H-H) -> n*(Na(3s)) interactions between the frontier MOs of both H-2 and the tetrametallic core of [{SiNDipp}MgNa](2).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin
Summary: The copper(i) alumanyl derivative reacts with up to three equivalents of various terminal alkynes, resulting in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate, and bis(alkynyl)aluminate derivatives. The alkene liberation process in the latter step is a unique case of alkyne transfer semi-hydrogenation.