Review
Chemistry, Organic
Lele Wang, Ziying Zhang, Huabin Han, Xiongli Liu, Zhanwei Bu, Qilin Wang
Summary: Bridged rings are commonly found in natural products and biologically active molecules, with significant applications in medicinal chemistry, natural product chemistry, synthetic chemistry, material chemistry, and life science. In recent years, new methods for the efficient synthesis of bridged compounds have been developed through the efforts of numerous chemists, providing useful reference for researchers in organic synthesis and related fields.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Albert Artigas, Cristina Castanyer, Nil Roig, Agusti Lledo, Miquel Sola, Anna Pla-Quintana, Anna Roglans
Summary: A synthetic methodology for functionalizing C-60 and C-70 fullerenes by cascading reactions has been reported. The resulting polyheterocyclic fullerene adducts can be potentially used in organic and perovskite photovoltaic devices.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Tianlong Zeng, Jingyang Kong, Hongkai Wang, Lingyan Liu, Weixing Chang, Jing Li
Summary: Substituent-controlled divergent cascade cycloaddition reactions of chalcones and arylalkynols in the presence of PtI2 were reported, yielding either spiroketals or oxa-bridged fused heterocycles depending on the substituent on the chalcone. Control experiments elucidated the high chemoselectivity, providing a method for the synthesis of a diverse array of structurally complex oxygen-containing heterocycles.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Yong-Liang Su, Geng-Xin Liu, Luca De Angelis, Ru He, Ammar Al-Sayyed, Kirk S. Schanze, Wen-Hao Hu, Huang Qiu, Michael P. Doyle
Summary: This study demonstrates the efficient generation of functionalized derivatives through photocatalyzed multicomponent reactions using nitrogen aromatic heterocycles, alkenes, and diazo compounds. The reaction shows high functional group tolerance and exacting regioselectivities. Mechanistic studies, including photophysical measurements, provide insights into this radical cascade reaction.
Article
Chemistry, Applied
Takeshi Yasui, Yuya Nakazato, Koutarou Kurisaki, Yoshihiko Yamamoto
Summary: In this study, a Rh-catalyzed asymmetric [2+2+2] cycloaddition reaction was reported, resulting in the synthesis of enantio-enriched tricyclic cyclohexadienes with a quaternary bridgehead carbon. It was found that the Rh-Phanephos complex was the most suitable catalyst, while Rh-biaryl bisphosphine catalysts were not applicable.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Guanqun Zhang, Abdullah S. Alshreimi, Laura Alonso, Alan Antar, Hsien-Cheng Yu, Shahidul M. Islam, Laura L. Anderson
Summary: A new method for the synthesis of 1-pyrrolines with high regio- and diastereoselectivity has been explored using N-alkenylnitrones and alkynes, with mechanistic studies providing insight into the balance of steric and electronic effects that control the product preferences. This cascade reaction demonstrates the divergent synthetic utility of the new method through diastereoselective derivatization of the 1-pyrrolines prepared.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Wang Wang, M. Kevin Brown
Summary: In this study, we achieved the stereoselective construction of 3D bicyclic scaffolds and azetidine derivatives by modulating N-sulfonylimines, allowing for either [4+2]- or [2+2]-cycloaddition reactions. The utility of the method was demonstrated through further modulation of the resulting products. Mechanistic studies supported a reaction mechanism involving Dexter energy transfer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Luyao Wang, Mengting Li, Zhitao Ning, Xi Zhang, Ying Fu, Zhengyin Du
Summary: An efficient visible-light-assisted, copper-catalyzed tandem radical cyclization of N-propargylindoles with cyclic ethers has been established. A series of 2-oxoalkyl-9H-pyrrolo[1,2-a]indol-9-ones with potential biological activities were synthesized in moderate yields using a dual catalytic system with copper acetate as a transition metal catalyst and eosin Y as a visible light catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Engineering, Environmental
Hao Yuan, Shuting Yi, Lufan Jia, Sicheng Chen, Ting Guo, Tao Meng
Summary: In this study, a living cell-inspired nanoscale multienzyme complex was designed to enable efficient cascade reactions and enhance the detection sensitivity of biosensors. The systematic study of this nanocomplex can inspire further investigation into the rules of cellular catalytic behaviors.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Physical
Yuwei Li, Li Liu, Hanying Zhao
Summary: By utilizing hydrophobic interaction, multienzyme proteinosomes are fabricated with p-gal, GOx, and HRP on the surfaces in a model system using PDEGMA and bovine serum albumin. The immobilized enzymes show higher bioactivities than the free enzymes, facilitating direct transfer of the product as a substrate from one enzyme molecule to another.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2022)
Review
Chemistry, Multidisciplinary
Guo-Qiang Xu, Peng-Fei Xu
Summary: In recent years, impressive progress has been made in the development of organic photoredox catalytic cascade reactions without the need for expensive and toxic transition metals, leading to the synthesis of chemically and biomedically valuable building blocks. This review highlights the recent advancements in this blooming area by introducing new catalytic cascade reactions mediated by organic photoredox catalysts and discussing their mechanisms and applications as reported in recent literature.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Deepak R. Mishra, Bhabani S. Panda, Sabita Nayak, Jasmine Panda, Seetaram Mohapatra
Summary: This review summarizes the significant progress and advances in the synthesis of 5-membered N-heterocycles through rhodium-catalyzed cascade reactions, including annulations, C-H/C-C activation, cycloaddition, rearrangement, cyclization, and metathesis, from 2018 to 2021.
Review
Chemistry, Multidisciplinary
Ruben Vicente
Summary: This review summarizes key reactivities relying on C-C bond cleavages of cyclopropenes, including both metal-catalyzed and metal-free transformations. The emphasis is on the synthetic utility and mechanistic aspects of various methodologies discussed, covering a range of reactions involving vinyl carbenes, metathesis processes, heterocycles syntheses, SEAr reactions, metalation-ring opening sequences, and cycloadditions. The focus is on results from 2007 to 2019, with relevant pioneering transformations eventually included.
Article
Chemistry, Organic
Shuai Zhao, Xiang-Xiang Chen, Nan Gao, Mingcheng Qian, Xin Chen
Summary: The cyclopropanation reaction of 3-diazooxindoles with arenes was successfully achieved for the first time using visible-light irradiation, leading to the synthesis of a series of spiro[norcaradiene-7,3'-indolin]-2'-ones with high yields and excellent diastereoselectivities. The synthetic utility of this catalyst-free photochemical methodology was further demonstrated through controllable rearrangement and epoxidation reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Li Li, Chenggang Mi, Guanwang Huang, Meirong Huang, Yuyi Zhu, Shao-Fei Ni, Zhaofeng Wang, Yong Huang
Summary: In this study, a new approach based on an I(III)/S(VI) reagent is described, which enables the cascade insertion of heteroatoms by sequentially generating two α-heteroatom-substituted metal carbenes in one reaction. This method allows for the synthesis of a wide range of α,α-O,O-, α,α-O,N-, and α,α-N,N-substituted ketones under mild conditions, and demonstrates the ability to simultaneously introduce multiple functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Nanoscience & Nanotechnology
A. R. Kytsya, L. I. Bazylyak, I. Yu. Zavaliy, Yu. V. Verbovytskyy, P. Zavalij
Summary: Bimetallic Ni-Cu nanoparticles with different (Ni/Cu) ratio were synthesized through a fast and simple reduction process in water/ethylene glycol solutions. The nanoparticles showed polydisperse sizes within 20-70 nm, with the particle diameter slightly depending on the Ni/Cu ratio. Additionally, XRD and EDX analyses revealed changes in lattice parameters and core-shell structure, respectively.
APPLIED NANOSCIENCE
(2022)
Article
Chemistry, Physical
Haifeng Zheng, Kan Wang, Isa Faghihi, Wendell P. Griffith, Hadi Arman, Michael P. Doyle
Summary: Metal-free electrophile addition to vinyl diazo compounds leads to highly selective formal [3 + 2] cyclization, 1,2-difunctionalization of alkenes, and C-H functionalization. Diverse electrophilic reagents can be used to generate highly reactive intermediates, enabling the synthesis of various substituted alpha-diazo esters with high yields and selectivities. Further transformations such as migration, oxidation, ring-expansion, and conjugate addition demonstrate the potential utility of this method.
Article
Chemistry, Multidisciplinary
Michael G. J. Doyle, Alexis L. Gabbey, Wesley McNutt, Rylan J. Lundgren
Summary: In this study, electron-deficient arylacetates were utilized as benzyl nucleophile surrogates to successfully generate enantioenriched acyclic molecules containing quaternary carbon centers via a two-step substitution-decarboxylation process. Products were often obtained with >90% ee using a commercially available catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Yong-Liang Su, Michael P. Doyle
Summary: α-Aminoalkyl radicals are easily synthesized and used as reaction activators to transform organic halides or sulfonium salts into highly reactive radical species. This review summarizes the emerging chemistry in the field, providing new pathways for transformations of halides and sulfonium salts.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Physical
Yong-Liang Su, Geng-Xin Liu, Luca De Angelis, Ru He, Ammar Al-Sayyed, Kirk S. Schanze, Wen-Hao Hu, Huang Qiu, Michael P. Doyle
Summary: This study demonstrates the efficient generation of functionalized derivatives through photocatalyzed multicomponent reactions using nitrogen aromatic heterocycles, alkenes, and diazo compounds. The reaction shows high functional group tolerance and exacting regioselectivities. Mechanistic studies, including photophysical measurements, provide insights into this radical cascade reaction.
Article
Chemistry, Organic
Gildardo Rivera, Luca De Angelis, Ammar Al-Sayyed, Soumen Biswas, Hadi Arman, Michael P. Doyle
Summary: A convenient, efficient, and inexpensive method has been developed for the synthesis of 1,2,3-triazine derivatives via deoxygenation of 1,2,3-triazine 1-oxide using trialkyl phosphites. This method provides a range of aromatic and aliphatic substituted 1,2,3-triazine-4-carboxylate derivatives cleanly in high yields. Unexpected 1,2,4-triazine derivatives were also obtained as minor products.
Article
Chemistry, Multidisciplinary
Ming Bao, Xiongda Xie, Jingjing Huang, Michael P. Doyle, Zhi Ren, Haibo Yue, Xinfang Xu
Summary: In this study, an Ag/Au-catalyzed cascade reaction of alkyne embedded diazoketones with indoles has been reported. Mechanistic studies indicate that the reaction involves a [4+2] cycloaddition followed by a retro-Michael addition/carbene N-H insertion process with gold catalysis, and a dearomatization/rearomatization sequence with silver catalysis, leading to the selective construction of N-doped polycyclic aromatic hydrocarbons (PAHs) with diverse structures and functional groups.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cascade reaction catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate. The reaction proceeds under mild conditions and provides the desired products in high yields and enantioretention. Furthermore, these dihydro-3H-carbazole-2-carboxylates can be transformed into decarboxylated compounds through hydrolysis and decarboxylation under unexpectedly mild reaction conditions, giving moderate yields with high retention of enantiomeric purity.
Article
Chemistry, Multidisciplinary
Luca De Angelis, Graham C. Haug, Gildardo Rivera, Soumen Biswas, Ammar Al-Sayyed, Hadi Arman, Oleg Larionov, Michael P. Doyle
Summary: One important reaction of 1,2,3-triazines is the inverse electron demand Diels-Alder (IEDDA) cycloaddition with a dienophile, which proceeds through nucleophilic addition to the triazine followed by N-2 loss and cyclization. Previous studies have not provided a comprehensive understanding of the site of nucleophilic addition on the triazine. This study investigated the C-, N-, H-, O-, and S-nucleophilic additions on 1,2,3-triazine and 1,2,3-triazine-1-oxide frameworks and revealed the differentiation of addition at the 4- and 6-positions. Computational studies further examined the factors influencing the outcomes of these reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Soumen Biswas, Luca De Angelis, Gildardo Rivera, Hadi Arman, Michael P. Doyle
Summary: 1,2,3-Triazine 1-oxides are highly effective substrates for inverse electron demand Diels-Alder reactions. These stable heterocyclic compounds, formed from vinyldiazoacetates via reaction with tert-butyl nitrite, undergo clean nucleophilic addition reactions with amidines to form pyrimidines, with beta-ketocarbonyl compounds and related nitrile derivatives to form polysubstituted pyridines, and with 3/5-aminopyrazoles to form pyrazolo[1,5-a]pyrimidines, in high yields. These reactions, catalyzed by bases, are rapid at room temperature and allow for a range of structural modifications.
Article
Chemistry, Organic
Michael P. Doyle, Ming Bao
Summary: This study achieved a highly enantioselective synthesis of substituted pyrrolidines and 1,2-oxazinanes via stereoretentive [3 + 2]/[3 + 3]-cycloaddition of nonracemic donor-acceptor cyclopropanes with imines, triazines, and nitrones. The reactions were conducted under mild conditions and showed good to high yields with broad applicability. Compared to previous approaches using racemic cyclopropane reactants and chiral ligand catalysts, this study utilized enantioenriched donor-acceptor cyclopropanes as reactants with achiral catalysts.
Article
Multidisciplinary Sciences
Luca De Angelis, Chao Pei, Ana L. Narro, Daniel Wherritt, Rene M. Koenigs, Michael P. Doyle
Summary: The synthesis and characterization of organic compounds with unique atom or functional group connectivity is a significant interest for chemists. Polycarbonyl compounds, in which multiple carbonyl groups are directly adjacent and influence each other's reactivity, have been extensively studied. However, little is known about 1,2,3,4-tetracarbonyl compounds. In this study, a synthesis strategy involving C-nitrosation of enoldiazoacetates is reported, which allows for the synthesis of 1,2,3,4-tetracarbonyl compounds where each carbonyl group is orthogonally masked.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Physical
Ming Bao, Michael P. Doyle
Summary: The [3+n]-cycloaddition reactions using chiral catalysts and racemic cyclopropanes or achiral catalysts and chiral, non-racemic cyclopropanes have proven to be important transformations for the synthesis of carbocyclic and heterocyclic compounds, showing both mechanistic and structural advantages in ring formation.
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cyclopentannulation-rearrangement cascade reaction. The reaction is catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate, and involves the use of 3-methylindole and non-racemic donor-acceptor cyclopropanes. The resulting products show high yields and enantioretention under mild reaction conditions, and further transformation into decarboxylated compounds can be achieved with moderate yields and high enantiomeric purity.
Review
Chemistry, Multidisciplinary
Michael G. J. Doyle, Rylan J. Lundgren
Summary: The Cu-catalyzed oxidative cross-coupling of N- and O-nucleophiles with aryl boronic acids (the Chan-Lam reaction) is a valuable method for preparing aniline and phenol derivatives, with high chemoselectivity and mild reaction conditions. In addition, we have developed the analogous carbon-carbon bond forming variant for the first time.
CHEMICAL COMMUNICATIONS
(2021)
