Article
Chemistry, Multidisciplinary
Niklas Radhoff, Constantin G. G. Daniliuc, Armido Studer
Summary: The design, synthesis, and application of benzene bioisosteres have been a subject of great interest in the past two decades. Recently, bicyclo[2.1.1]hexanes have been established as highly attractive bioisosteres for ortho- and meta-substituted benzenes. In this study, we present a mild, scalable, and transition-metal-free method for constructing highly substituted bicyclo[2.1.1]hexan-2-ones through Lewis acid-catalyzed (3+2)-cycloaddition of bicyclo[1.1.0]-butane ketones with disubstituted ketenes. The reaction exhibits high functional group tolerance, as evidenced by the successful synthesis of various 3-alkyl-3-aryl and 3,3-bisalkyl bicyclo[2.1.1]hexan-2-ones (26 examples, up to 89% yield). Additionally, postfunctionalization of the exocyclic ketone moiety is demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jun Li, Scott R. Gilbertson
Summary: This study reports a diastereoselective [4 + 2] cycloisomerization of asymmetric allenyl dienes synthesized using Ma's method. These substrates undergo diastereoselective intramolecular rhodium catalyzed [4 + 2] cycloisomerization similar to thermal intramolecular Diels-Alder reactions, with diastereoselectivities ranging from 99:1 to 90:10 in most examples out of 29 presented.
Article
Chemistry, Organic
Ye Qiu, Zhi-Qin Liang, Kun-Quan Chen, Lei Dai, Song Ye
Summary: We developed an enantioselective N-heterocyclic carbene (NHC)-catalyzed rearrangement of enol epsilon-lactones for the construction of bicyclic beta-lactones. The reaction works well for both exo- and endo-enol epsilon-lactones, giving the corresponding bicyclic beta-lactones with two or three contiguous stereocenters, respectively. The reaction features readily available starting materials, 100% atom economy, mild conditions, high diastereo- and enantioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Melanie A. Drew, Andrew J. Tague, Christopher Richardson, Stephen G. Pyne, Christopher J. T. Hyland
Summary: A two-step Pd-catalyzed (3 + 2) cycloaddition/HNO2 elimination reaction sequence has been developed to efficiently produce novel cyclic 1,3-dien-5-yne systems with high atom efficiency. The research allows for the selective isolation of a single diastereoisomer of the cycloadduct, demonstrating the potential for practical applications in organic synthesis.
Article
Chemistry, Organic
Yuan-Yuan Xu, Lei Dai, Zhong-Hua Gao, Song Ye
Summary: The e-benzylation of gamma-alkenyl-gamma-oxidized enals via dual photoredox and N-heterocyclic carbene catalysis has been developed, providing moderate to good yields of e-benzyl-alpha,fi-gamma,(5-bisunsa-turated esters with exclusive regioselectivities. The reaction is proposed to proceed through the generation of a benzyl radical under photocatalysis, followed by its addition to an NHC-bound trienolate intermediate.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Soumen Pandit, Vinay Kumar Pandey, Amit Singh Adhikari, Suresh Kumar, Arvind Kumar Maurya, Ruchir Kant, Nilanjana Majumdar
Summary: An efficient method has been developed for the construction of hydrocarbazoles bearing three continuous sterically hindered stereocenters via a highly diastereoselective palladium-catalyzed [4 + 2]-cycloaddition/ dearomatization of 3-nitroindoles. The multifaceted transformations of the products demonstrate the further synthetic utility of this method. The catalytic asymmetric aspect of this transformation has also been explored.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Soumen Pandit, Vinay Kumar Pandey, Amit Singh Adhikari, Suresh Kumar, Arvind Kumar Maurya, Ruchir Kant, Nilanjana Majumdar
Summary: An efficient method for the construction of hydrocarbazoles bearing three continuous sterically hindered stereocenters has been developed using a diastereoselective palladium-catalyzed [4 + 2]-cycloaddition/dearomatization reaction. The reaction occurs at ambient conditions with the formation of a 1,4-zwitterionic intermediate from gamma-methylidene-delta-valerolactones. The synthetic utility of this method is demonstrated by the various transformations possible from the products, and the catalytic asymmetric aspect has also been explored.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ling Li, Xiu-Shuai Chen, Xiang-Ping Hu
Summary: In this study, an intramolecular Cu-catalyzed asymmetric propargylic [4 + 2] cycloaddition reaction was achieved using a chiral tridentate N-ligand as the catalyst, leading to chiral tetrahydroisoindolo[2,1-a]quinoxalines with high yields and good to excellent enantioselectivities. The reaction is efficient, simple, and has a broad substrate scope, providing a powerful and concise strategy for the stereoselective synthesis of optically active polycyclic heterocycle frameworks.
Article
Chemistry, Organic
Chaoshui Liu, Qiuzi Dai, Yaqian Li, Chuhan Huang, Lijuan Guo, Zi Yang
Summary: A novel protocol for synthesizing N-alkylindoles using readily available N-nitrosoanilines and iodoniumylides through the rhodium-(III)-catalyzed C-H bond activation/intramolecular cyclization reaction has been described. This strategy employs nitroso as a traceless directing group. The transformation shows powerful reactivity, tolerates various functional groups, and proceeds with moderate yields under mild reaction conditions, providing a straightforward approach to access structurally diverse and valuable N-alkyl indole derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yuan-Yuan Xu, Zhong-Hua Gao, Cao-Bo Li, Song Ye
Summary: The enantioselective alpha-oxidative coupling of enals with carboxylic acids was achieved by umpolung of an NHC-bound enolate with an iodine(III) reagent. The reaction produced alpha-acyloxyl-beta,gamma-unsaturated esters in good yields, with high regio- and enantioselectivities. The reaction involved the formation of an enol iodine(III) intermediate from the enolate with iodosobenzene, which changed the polarity of the enal's alpha-carbon from nucleophilic to electrophilic and facilitated the subsequent carboxylate addition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Hui-Hui Wu, Xiao-Zu Fan, Zhe Tang, Heng Zhang, Lu-Yu Cai, Xiao-Fan Bi, Hong-Wu Zhao
Summary: Under specific reaction conditions, the (5 + 6) cycloaddition of vinylethylene carbonates with isatoic anhydrides proceeded smoothly, yielding medium-sized N,O-containing heterocycles in reasonable chemical yields, as confirmed by X-ray diffraction analysis.
Article
Chemistry, Multidisciplinary
Vishal Suresh Kudale, Ching-Piao Chu, Jeh-Jeng Wang
Summary: This study developed a novel method for the selective nitrosation of imidazo[1,2-a]pyridine derivatives using AgNO3 as a NO source. The protocol showed low toxicity, mild reaction conditions, and broad functional group tolerance, making it significant for synthetic transformations and gram-scale experiments.
NEW JOURNAL OF CHEMISTRY
(2022)
Review
Chemistry, Applied
Daksh Singh Davas, Srashti Bhardwaj, Raju Sen, Dinesh Kumar Gopalakrishnan, Janakiram Vaitla
Summary: This review surveys the coupling of two carbene precursors for the synthesis of alkenes. The key factor for selective carbene coupling is the difference in carbene generation rate between the two precursors. This strategy requires careful selection of precursors and fine-tuning of reaction conditions to achieve the desired chemo- and stereoselectivity. The review covers inter- and intramolecular coupling of diazo compounds as well as cross-coupling between diazo and non-diazo compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Biochemistry & Molecular Biology
Camilo Morales-Manrique, Edwin A. Baquero, James Guevara-Pulido
Summary: In recent years, N-heterocyclic carbenes (NHCs) have been recognized as versatile organocatalysts for the activation of aldehydes, leading to the production of 3,4-dihydropyran-2-ones and related derivatives. This review provides an overview of the organocatalytic processes involving NHCs in synthesizing these compounds over the past eight years. These processes utilize various substrates, catalysts, and reaction conditions, mainly focusing on [4+2] and [3+3] cycloadditions to generate the desired skeleton with biological activity and multiple stereocenters. The resulting products can be scaled up and further modified for potential applications in the field of biology.
Article
Chemistry, Organic
Pengrui Jiang, Jingcheng Guo, Minghua Gong, Xiangui Zhou, Wei Cao, Zhenqian Fu, Wei Huang
Summary: A novel N-heterocyclic carbene-catalyzed annulation reaction of bromoenals with 2-aminochromones has been successfully developed, leading to the efficient synthesis of structurally diverse chromeno[2,3-b]pyridinones in acceptable to excellent yields. The reaction features mild conditions, a broad substrate scope, and easy scalability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Xiaojian Ren, Lei Zhu, Yinghua Yu, Zhi-Xiang Wang, Xueliang Huang
Article
Chemistry, Organic
Jibing Liu, Lei Zhu, Wan Wan, Xueliang Huang
Article
Chemistry, Multidisciplinary
Yinghua Yu, Liyao Ma, Jiajin Xia, Luoting Xin, Lei Zhu, Xueliang Huang
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Review
Chemistry, Organic
Fulin Zhang, Luoting Xin, Yinghua Yu, Saihu Liao, Xueliang Huang
Summary: This review summarizes the significance and methods of transition-metal-catalyzed bridging C-H activation in chemical synthesis, with a particular focus on the role of alkenes, alkynes, and metal carbenes as intermediates in the activation process.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Physical
Luoting Xin, Wan Wan, Yinghua Yu, Qiuling Wan, Liyao Ma, Xueliang Huang
Summary: The study presents a novel method for the synthesis of pyridoisoquinolinone derivatives using pyridotriazoles and o-bromo/pseudohalo benzaldehydes. This method is efficient and provides a rapid route to prepare protoberberine-type alkaloids. The pyridotriazole plays a dual role in promoting C-H bond functionalization and constructing the polycyclic system through pyridine dearomatization.
Article
Chemistry, Applied
Liyao Ma, Yinghua Yu, Luoting Xin, Lei Zhu, Jiajin Xia, Pengcheng Ou, Xueliang Huang
Summary: A novel synthesis method is described in this work, where acylsilanes are coupled with aldehydes under visible light to produce alpha-hydroxyketones without the need for a photosensitizer or any other additives. The reaction can occur at ambient temperature with low energy visible light irradiation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Qiuling Wan, Luoting Xin, Jian Zhang, Xueliang Huang
Summary: This study describes a gold-catalysed cycloisomerization of 1,5-diynes, providing a selective access to 1,3,4-trisubstituted pyrroles. The cationic gold catalyst activates the ynamide moiety, initiating the cycloisomerization to produce the pyrrole core. Water acts as an external nucleophile to trap the vinyl cationic species, leading to the formation of 1,3,4-trisubstituted pyrroles with high selectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Ryan T. Kenny, Fei Liu
Summary: A robust synthesis of Soai-type pyrimidine aldehydes was achieved by controlled formation and quenching of a lithiated pyrimidine intermediate. The optimized rate of n-BuLi addition synchronized with the addition to ethyl formate, resulting in consistently high yields of 2-alkylpyrimidinecarboxaldehydes, which can be used in autocatalysis or as functionalized synthons.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jinling Liu, Yinghua Yu, Xueliang Huang
Summary: Deuterated compounds are important in pharmaceutical chemistry and the selective incorporation of deuterium atoms onto pharmacophore-containing compounds is of great interest. In this study, a concise method for constructing deuterated dibenzo-fused epsilon-lactones and epsilon-lactams through Pd-catalyzed carbene bridging C-D bond activation strategy was described. Deuterated ortho-bromobenzaldehydes were readily available reactants and deuterium atoms were selectively incorporated at the dibenylic position with high deuterated ratio.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jiajin Xia, Jibing Liu, Yinghua Yu, Jian Zhang, Xueliang Huang
Summary: This study presents an unprecedented gold-catalyzed oxidative Buchner-type cyclopropanation, allowing the cycloisomerization of diynamides and the synthesis of diverse N-heterocyclic products with challenging structural skeletons.
Article
Chemistry, Organic
Pengcheng Ou, Lei Zhu, Yinghua Yu, Liyao Ma, Xueliang Huang
Summary: In this study, a Xantphos-containing dinuclear palladium complex was used to catalyze the geminal aminoallylation of diazocarbonyl compounds, providing a selective synthesis of various quaternary alpha-amino esters. The reaction did not proceed through direct N-H insertion, allylic alkylation of amino nucleophiles, or diene formation. Mechanistic investigations indicated that a relayed pathway via allylation or a [2,3]-sigmatropic rearrangement was unlikely.
Article
Chemistry, Multidisciplinary
Mingruo Ding, Pengcheng Ou, Xuening Li, Yinghua Yu, Mengmeng Niu, Yongjian Yang, Yewei Huang, Zhi-Xiang Wang, Xueliang Huang
Summary: Through space palladium/hydrogen shift is an efficient strategy for selective functionalization of a specific remote C-H bond. This study investigates the relatively less explored 1,5-Pd/H shift pattern between a vinyl and an acyl group, leading to the rapid synthesis of 5-membered-dihydrobenzofuran and indoline derivatives. The study also reveals a trifunctionalization of a phenyl ring through 1,5-palladium migration relayed decarbonylative Catellani type reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jiajin Xia, Baolong Zhu, Qiuling Wan, Yinghua Yu, Shenlin Huang, Jian Zhang, Xueliang Huang
Summary: Transition metal-catalyzed divergent synthesis through alternation of the catalyst is demonstrated, providing an operationally simple way to access different valuable products from the same reactants. A gold-catalyzed cascade reaction of conjugated diynamides with allylic alcohols is described, giving selectively substituted allenes and furans by varying the catalysts. Mechanistic studies reveal a [3,3]-sigmatropic rearrangement and an intramolecular Himbert arene/allene Diels-Alder cycloaddition as additional reaction sequences to access dearomatized products with bicyclo[2,2,2]octadiene core.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Fulin Zhang, Ruihua Zhao, Lei Zhu, Yinghua Yu, Saihu Liao, Zhi-Xiang Wang, Xueliang Huang
Summary: The formation of a five membered palladacycle enables the selective activation of a proximal C-H bond in the aldehyde moiety and the construction of a valuable isoindolinone framework. Variation of the reaction conditions allows for the selective formation of three types of isoindolinones. Mechanistic studies provide insights into the reaction pathways, and the synthetic potential of this methodology is demonstrated through the concise routes to key intermediates of various compounds.
CELL REPORTS PHYSICAL SCIENCE
(2022)
Article
Chemistry, Organic
Wan Wan, Jibing Liu, Xueliang Huang
Summary: A novel approach to synthesizing 4-oxo-but-2-ynamides through gold-catalyzed selective oxidation of 1,3-diynamides has been developed. The products possess activated C-C triple bond and serve as versatile building blocks in synthetic community. The method provides a range of 4-oxo-but-2-ynamide derivatives in moderate to high yields, with the absence of traditional 1,2-dicarbonyl type products.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
