Article
Chemistry, Physical
Maxwell G. Holl, Tristan H. Lambert
Summary: The ring-opening carbonyl-olefin metathesis of cyclobutenes can be used to synthesize a variety of aldehydes, and the bistrifluoroacetic acid salt of 2,3-diazabicyclo[2.2.2]octane is an efficient catalyst for promoting these reactions.
Article
Chemistry, Multidisciplinary
Chen Chen, Xing-Xing Yang, Zhi Zhao, Bo Han, Wei Du, Ying-Chun Chen
Summary: In this study, the normal 1,3-dipolar cycloaddition between the carbonates of 4-hydroxy-2-cyclopentenones and C,N-cyclic azomethine imines was switched to an inverse-electron-demand version under Pd(0) catalysis. This transformation was achieved by in situ generation of HOMO-raised eta(2)-Pd(0)-cyclopentadienone complexes. The researchers constructed a variety of fused heterocyclic architectures with high levels of diastereo and enantioselectivity. Furthermore, diastereodivergent synthesis was realized by tuning the bifunctional phosphine ligands. A similar reaction with in situ formed thiophene-1,1-dioxide was also compatible by using a chiral bisphosphine ligand, leading to the formation of fused cyclic sulfone frameworks with high stereoselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Guipeng Feng, Guoyang Ma, Wenyan Chen, Shaohong Xu, Kaikai Wang, Shaoyan Wang
Summary: The [3 + 2] 1,3-dipolar cycloaddition of C,N-cyclic azomethine imines with allyl alkyl ketones has been achieved, resulting in a range of tetrahydroisoquinoline derivatives with good diastereoselectivities and enantioselectivities. The absolute configuration of the product was determined using quantum electronic circular dichroism calculation and ECD spectrum method.
Article
Chemistry, Multidisciplinary
Guangjun Bao, Peng Wang, Guofeng Li, Changjun Yu, Yiping Li, Yuyang Liu, Zeyuan He, Tiantian Zhao, Jing Rao, Junqiu Xie, Liang Hong, Wangsheng Sun, Rui Wang
Summary: A new method for 1,3-dipolar cycloaddition reactions between different types of amino acids to generate various quaternary amino acids was disclosed in this study. This method can also be applied within peptide chains, providing a new approach for late-stage peptide modification and drug conjugation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Jose Cortes Vazquez, Jacqkis Davis, Vladimir N. Nesterov, Hong Wang, Weiwei Luo
Summary: A formal [3 + 3] cyclization reaction has been developed for the synthesis of 1,3,4-oxadiazinanes with generally high yields (up to 96%). The reaction, catalyzed by Sc(OTf)(3), has a broad substrate scope for both diaziridines and quinones. The synergistic activation of 1,3-dipolar diaziridines and dipolar quinones was found to be essential for enabling this reaction.
Article
Chemistry, Organic
Arthur Lebrene, Thomas Martzel, Laura Gouriou, Morgane Sanselme, Vincent Levacher, Sylvain Oudeyer, Carlos Afonso, Corinne Loutelier-Bourhis, Jean-Francois Briere
Summary: A straightforward method for synthesizing original 1,6-diazabicyclo[4.3.0]nonane-2,7-diones was developed using a DBU-organocatalyzed multicomponent Knoevenagel-aza-Michael-Cyclocondensation reaction. Analysis of key reactive intermediates using mass spectrometry confirmed the proposed mechanism.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Jing Huang, Bo Jiang, Xiyuan Zhang, Yanfeng Gao, Xiufang Xu, Zhiwei Miao
Summary: A synthetic strategy for accessing functionalized azabicyclo[3.3.1]alkenones with three tertiary stereocenters has been developed. The method is scalable and the products can be transformed to various eight-membered-ring bridged heterocyclic molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
A. P. Molchanov, M. M. Efremova, M. A. Kuznetsov
Summary: This review summarizes the main results of cycloaddition reactions involving cyclopropenes and methylenecyclopropanes, which are compounds with strained three-membered rings and endo- and exocyclic double bonds. The focus is primarily on their reactions with 1,3-dipoles, resulting in complex heterocyclic systems with high regio- and stereoselectivity.
RUSSIAN CHEMICAL BULLETIN
(2022)
Article
Chemistry, Organic
Yuji Nishiura, Kevin J. Gonzalez, Alexander Q. Cusumano, Brian M. Stoltz
Summary: Spirocyclic scaffolds are important motifs that can have favorable effects on pharmaceutical compounds. This study reports a high-yielding and enantioselective method for synthesizing chiral spirocyclic heterocycles.
Article
Chemistry, Multidisciplinary
Phong K. Quach, Jesse H. Hsu, Ivan Keresztes, Brett P. Fors, Tristan H. Lambert
Summary: The ring-opening metathesis polymerization of cyclopropenes using hydrazonium initiators was investigated. The initiators, formed by condensing 2,3-diazabicyclo[2.2.2]octane and an aldehyde, polymerize cyclopropene monomers through a sequence of [3+2] cycloaddition and cycloreversion reactions. The study showed that the monomer to initiator ratio had a positive correlation with the degree of polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jackson S. Henneveld, Farshad Shiri, Alireza Ariafard, Nigel T. Lucas, Alex C. Bissember, Bill C. Hawkins
Summary: The investigation and formalization of the distinctive dipole-transmissive dipolar cycloaddition (DTDC) methodology is reported. A DTDC procedure was developed by taking advantage of the structural complementarity of azide and diazoalkane 1,3-dipoles. This method allows for the rapid construction of functionalized polycyclic N-heterocycles through intramolecular azide-alkene 1,3-dipolar cycloadditions followed by N-derivatization and subsequent 1,3-dipolar cycloadditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Sha Li, Yahan Sun, Xiaofang Li, Oskar Smaga, Sebastian Koniarz, Marcin Stepien, Piotr J. Chmielewski
Summary: A 1,3-cycloaddition reaction between 2-(tert-butyl)-8H-isoquinolino[4,3,2-de]phenanthridin-9-ium chloride and Ni-II norcorrole in the presence of base has been demonstrated to yield a family of chiral derivatives fused with pyrrole subunits of the macrocycle. Dehydrogenation of the cycloaddition products leads to dibenzoullazine ortho-fused antiaromatic porphyrinoids.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Gang Wang, Jiang Wu, Yi Li, Zicheng Huang, Jing Zou, Zhao-Lin He
Summary: A cross-1,3-dipolar cycloaddition reaction between α-halohydroxamates (azaoxyallyl cations generated in situ) and N,N'-cyclic azomethine imines was developed. The synthetic protocol provided a facile and rapid access to pyrazolo[1,2-a][1,2,4]triazine derivatives with good yields and excellent diastereoselectivities under mild metal-free conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
M. Mohamed Arshath Ali, G. Udhaya Suriyan, K. Jaga Surya, Kailasam Saravana Mani
Summary: A multicomponent reaction improves the efficiency and economy of the reaction process. Pyrrolidine-derived heterocycles are important scaffolds for anticancer drugs. Scientists created pyrrolizine derivatives and tested their antitumor activity against various cancer types using Mitomycin C as inspiration.
JOURNAL OF HETEROCYCLIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Tuong Anh To, Binh Khanh Mai, Thanh Vinh Nguyen
Summary: This article reports a new Bronsted acid-catalyzed carbonyl-olefin metathesis reaction using nitromethane as a solvent, which can promote intramolecular ring-closing reactions.
Article
Chemistry, Multidisciplinary
Tao Shen, Tristan H. Lambert
Summary: A method for C-H bond amination via electrophotocatalytic Ritter-type reaction has been developed, catalyzed by a trisaminocyclopropenium (TAC) ion in an electrochemical cell under irradiation, converting benzylic C-H bonds to acetamides without stoichiometric chemical oxidant. The method demonstrates compatibility with a wide range of functionalities and shows successful transformation of several complex substrates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Ilana Stone, Rachel L. Starr, Yaping Zang, Colin Nuckolls, Michael L. Steigerwald, Tristan H. Lambert, Xavier Roy, Latha Venkataraman
Summary: This Review discusses recent advancements in utilizing scanning probe techniques for chemical bond formation and cleavage at nanoscale electrodes, emphasizing the implications for synthetic chemistry and future research.
NATURE REVIEWS CHEMISTRY
(2021)
Article
Chemistry, Organic
Keri A. Steiniger, Tristan H. Lambert
Summary: A new method for efficient and regioselective hydrosilylation of epoxides using a PCCP nickel complex and Lewis acid co-catalyst has been reported, leading to the formation of unbranched, primary alcohols from terminal, monosubstituted epoxides. The method is shown to work with a variety of substrates, both terminal and nonterminal epoxides, and a mechanistic rationale is provided for this novel use of a PCCP derivative as a ligand for transition-metal catalysis.
Article
Chemistry, Multidisciplinary
Eun Kee Cho, Phong K. Quach, Yunfei Zhang, Jae Hun Sim, Tristan H. Lambert
Summary: The use of hydrazine-catalyzed ring-closing carbonyl-olefin metathesis (RCCOM) to synthesize polycyclic heteroaromatic (PHA) compounds is described in this article. It is shown that substrates containing Lewis basic functionalities such as pyridine rings and amines, which inhibit acid catalyzed RCCOM reactions, are compatible with this reaction. By using a catalyst loading of 5 mol%, a variety of PHA structures can be synthesized from biaryl alkenyl aldehydes prepared by cross-coupling.
Article
Chemistry, Multidisciplinary
Phong K. Quach, Jesse H. Hsu, Ivan Keresztes, Brett P. Fors, Tristan H. Lambert
Summary: The ring-opening metathesis polymerization of cyclopropenes using hydrazonium initiators was investigated. The initiators, formed by condensing 2,3-diazabicyclo[2.2.2]octane and an aldehyde, polymerize cyclopropene monomers through a sequence of [3+2] cycloaddition and cycloreversion reactions. The study showed that the monomer to initiator ratio had a positive correlation with the degree of polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Maxwell G. Holl, Tristan H. Lambert
Summary: The ring-opening carbonyl-olefin metathesis of cyclobutenes can be used to synthesize a variety of aldehydes, and the bistrifluoroacetic acid salt of 2,3-diazabicyclo[2.2.2]octane is an efficient catalyst for promoting these reactions.
Article
Chemistry, Multidisciplinary
He Huang, Keri A. Steiniger, Tristan H. Lambert
Summary: This Perspective highlights recent advances in the area of electrophotocatalysis, which combines the power of light and electrical energy to realize new catalytic transformations. Electrophotocatalysis offers the ability to perform potent yet selective redox reactions under relatively mild conditions, without the need for large quantities of chemical oxidants or reductants.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Rebecca M. Wilson, Tristan H. Lambert
Summary: This article introduces the use of cyclopropenium ions as a key element in the design of novel catalysts. The unique properties of cyclopropenium ions make them versatile building blocks for highly reactive catalysts. The article describes the applications of cyclopropenium ions in various reactions, including promoting dehydrative reactions, acting as organic Bronsted bases and phase-transfer catalysts, and serving as electrophotocatalysts for oxidation reactions.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
He Huang, Tristan H. Lambert
Summary: A method for the regiodivergent aminooxygenation of aryl olefins under electrophotocatalytic conditions is described, which utilizes a trisaminocyclopropenium ion catalyst and visible light irradiation to convert aryl olefins to oxazoline products with high selectivity. By choosing between water and urethane as reagents, different derivatives of 2-amino-1-ol or 1-amino-2-ol can be synthesized from the same substrate.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Scott W. Spring, Jesse H. Hsu, Renee J. Sifri, Szu-Ming Yang, Chloe S. Cerione, Tristan H. Lambert, Christopher J. Ellison, Brett P. Fors
Summary: Creating strong and tough plastics from sustainable and biorenewable resources is a significant challenge. In this study, we synthesized a thermoplastic material, poly(2,3-dihydrofuran) (PDHF), using a metal-free cationic polymerization process. PDHF exhibited high tensile strength, toughness, optical clarity, and barrier properties, making it suitable for various applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Amymarie K. Bartholomew, Ilana B. Stone, Michael L. Steigerwald, Tristan H. Lambert, Xavier Roy
Summary: The direct conversion of solar energy to mechanical work is a more efficient energy solution for the future. Researchers have discovered a new crystal material that can continuously roll under sunlight, driven by blue-light reactions. This finding introduces a new strategy for manipulating the electronic properties of chromophores and demonstrates the ability to convert solar energy to continuous physical motion using easily accessible molecular systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Tao Shen, Yi-Lun Li, Ke-Yin Ye, Tristan H. Lambert
Summary: Oxygen-containing functional groups are found in complex small molecules. The selective oxygenation of contiguous C-H bonds to form multiple C-O bonds has been mainly achieved through biosynthesis. However, this study demonstrates the successful synthetic oxygenation of two or three contiguous C-H bonds using electrophotocatalysis, with high selectivity and avoidance of overoxidation risk.
Article
Chemistry, Multidisciplinary
Keri A. Steiniger, Matthew C. Lamb, Tristan H. Lambert
Summary: This study presents a method for C-(sp(3))-C-(sp(3)) cross-coupling of amines. Primary amines are transformed into 1,2-dialkyldiazenes by reacting with O-nosylhydroxylamines in the presence of atmospheric oxygen. The denitrogenation of diazenes using an iridium photocatalyst forms the C-C bond. The substrate scope is broad, allowing for various functional groups, such as heteroaromatics and unprotected alcohols and acids.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Keri A. Steiniger, Tristan H. Lambert
Summary: A new tandem electrochemical/electrophotocatalytic reaction is developed to olefinate aldehydes and ketones with a broad range of unactivated alkenes under nonbasic conditions. This method involves the oxidation-induced denitrogenation of cyclic diazenes to form stable 1,3-distonic radical cations that rearrange to yield the olefin products.
Article
Chemistry, Multidisciplinary
Ilana B. Stone, Rachel L. Starr, Norah Hoffmann, Xiao Wang, Austin M. Evans, Colin Nuckolls, Tristan H. Lambert, Michael L. Steigerwald, Timothy C. Berkelbach, Xavier Roy, Latha Venkataraman
Summary: This study describes the Ullmann coupling of aryl iodides on rough gold surfaces, investigations of the reaction mechanism using experimental and theoretical methods reveal the influence of surface roughness and local electric fields on the reaction, providing important insights for understanding catalysis.
