Article
Chemistry, Organic
Xiaoqin Ning, Yongke Chen, Fangdong Hu, Ying Xia
Summary: This study presents the palladium-catalyzed cross-coupling reactions of cyclobutanone-derived N-sulfonylhydrazones with aryl or benzyl halides, demonstrating that the metal carbene process and beta-hydride elimination can occur smoothly in strained ring systems to yield structurally diverse products. The preliminary success in asymmetric carbene coupling reactions in strained ring systems offers a promising route for the synthesis of enantioenriched four-membered-ring molecules.
Article
Chemistry, Organic
Ruwei Shen, Kaixin Yin, Yishuai Fan
Summary: The copper-catalyzed reaction of alpha-halo-N-tosylhydrazones with H-phosphoryl compounds provides alkenylphosphoryl compounds with moderate to good yields. This reaction may proceed via a copper-promoted Bamford-Stevens-type reaction of an alpha-phosphorylated diazo intermediate. In the absence of a copper catalyst, the diazo intermediate is trapped by an excess H-phosphoryl compound to form alpha, N-bisphosphoryl hydrazone.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Guofeng Zhao, Yi Wu, Hai-Hong Wu, Junfeng Yang, Junliang Zhang
Summary: This study presents a Pd-catalyzed enantioselective three-component coupling for the synthesis of chiral diarylmethyl alkynes using a novel chiral ligand. The method features readily available starting materials, high enantioselectivity, and ease of operation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Qing Wang, Xiangzhang Tao, Shengyang Ni, Yi Pan, Yi Wang
Summary: Bimolecular nucleophilic substitution S(N)2 is the earliest and most important means of amination of alkyl electrophiles, but its practical utilization is mostly limited to primary or activated substrates. Establishing C(sp(3))-N bonds from alkyl substrates in cross-coupling chemistry using palladium and nickel catalysts has been a persistent challenge. The existing routes are restricted to copper catalysis and photoredox catalysis. In this study, we demonstrate an alternative amination strategy that rapidly constructs C(sp(3))-N bonds from accessible alkyl electrophiles by utilizing Nickel (III) species reductive eliminations under high efficiency catalysis.
Article
Chemistry, Organic
Ziwei Huang, Zirui Lin, Jiexiong Mai, Shaohuan Lv, Feng Xie, Youxue Yuan, Wenbing Zhang, Fan Qian, Bin Li
Summary: This study describes a convenient and practical method for the synthesis of 2-cyano and 2-ester anilines via efficient and selective copper-catalyzed reductive amination. These compounds were successfully synthesized with good functional group tolerance. Furthermore, the synthesized compounds exhibited excellent fluorescent properties, which may have potential applications in the development of near-ultraviolet optical devices.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Fengqian Zhao, Han-Jun Ai, Xiao-Feng Wu
Summary: In this study, a novel copper-catalyzed method has been developed for the highly selective double carbonylation of alkyl bromides, yielding moderate to good yields of alpha-keto amides as the sole products. Under different conditions, controllable double- and mono-carbonylation can be achieved with alkyl iodides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Wenxin Lu, Qinglei Chong, Fanke Meng
Summary: A catalytic method for the construction of homoallylic alcohols from trans-1,3-dienes and anhydrides is presented. This method involves the generation of enantiomerically enriched allyl-Cu species which react selectively with a wide range of anhydrides. The functionalization of homoallylic alcohol products provides useful building blocks that are difficult to obtain through other methods.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Chao Hong, Shuling Yu, Zhanxiang Liu, Yuhong Zhang
Summary: A coupling reaction of acrylic acids/benzoic acids with alpha-diazocarbonyl compounds has been achieved using a combined catalytic system of rhodium catalyst and Zn(OAc)(2) additive. The presence of Zn(OAc)(2) facilitates the C(sp(2))-H activation and disrupts the formation of carboxylic ester via nucleophilic O-H insertion to metal carbenoid. This method offers mild reaction conditions and broad substrate scope, providing a convenient and direct approach for the synthesis of alpha-pyrones and isocoumarins without the need for carboxylic acid transformation to amides.
Article
Chemistry, Physical
Lu Ouyang, Rui Miao, Zhanhui Yang, Renshi Luo
Summary: Our Ir-catalyzed reductive amination of carboxylic acids with amines allows for the production of structurally diverse N-alkylated amines in good to excellent yields (up to 60 examples). This method offers mild conditions, convenient operations, and excellent functional group tolerance. The synthesis of Cinacalcet and (R)-Fendiline highlights the synthetic value of this protocol.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Matthias Elfinger, Timon Schoenauer, Sabrina L. J. Thomae, Robert Staeglich, Markus Drechsler, Mirijam Zobel, Juergen Senker, Rhett Kempe
Summary: The 3D metal catalyst developed here utilizes hydrogen as the reducing agent and easily handled ammonia dissolved in water as the nitrogen source for the synthesis of primary amines. The catalyst operates under mild conditions and outperforms commercially available noble metal catalysts. The key to its high activity is the unique support material it uses.
Article
Chemistry, Physical
Jichao Xiao, John Montgomery
Summary: A simple procedure for the nickel-catalyzed defluorinative alkylation of unactivated aliphatic aldehydes is reported. The protocol exhibits broad substrate scope, mild conditions, and a simple catalytic setup.
Article
Chemistry, Applied
Packirisamy Kuzhalmozhi Madarasi, Chinnappan Sivasankar
Summary: This study reports the reductive coupling of diazo compounds through terminal nitrogen using a copper-dppf catalyst. Control experiments revealed that the formation of a copper-Mg heterobimetallic complex was responsible for the observed reactivity pattern. The reaction produced diazines as the coupling product along with biphenyl.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Francisco Villalba, Ana C. Albeniz
Summary: Hydrazones play a crucial role as ligands in palladium-catalyzed cross coupling reactions, but their interaction with palladium and reaction mechanism remain understudied.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Dattatri, Maneesh Kumar Reddy Singam, Jagadeesh Babu Nanubolu, Maddi Sridhar Reddy
Summary: A cascade reaction of enynones with enaminones via carbene insertion and aryl migration is reported in this study, which efficiently constructs distinctive multisubstituted furans with an all-carbon quaternary center. The protocol can be extended to synthesize furano-pyrrole bis-heterocycles in the same pot. The heterogeneity of this reaction was demonstrated by generating divergent chemical space under relatively mild reaction conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Physical
Chao-Yang Zhao, Ding-Wei Ji, Hao Zheng, Gu-Cheng He, Heng Liu, Yan-Cheng Hu, Qing-An Chen
Summary: This study developed a Pd-catalyzed redox divergent coupling of ketones with terpenols, controlling the oxidation states of the product by employing different additives and highlighting the practicality of the protocol with gram-scale reactions and low catalyst loading. Detailed experimental studies were also conducted to elucidate the reaction mechanism and factors influencing redox selectivity. This coupling protocol provides an important complement to known precedents in Tsuji-Trost allylation of ketones.
Article
Chemistry, Medicinal
Shannon Pecnard, Olivier Provot, Helene Levaique, Jerome Bignon, Laurie Askenatzis, Francois Saller, Delphine Borgel, Sophie Michallet, Marie-Catherine Laisne, Laurence Lafanechere, Mouad Alami, Abdallah Hamze
Summary: A series of cyclic bridged analogs of isocombretastatin A-4 with compound 42 showed high antiproliferative activity against a panel of cancer cell lines, as well as strong activity against colon-carcinoma cells and MDR1-overexpressing K562R cell line. Compound 42 also effectively inhibited tubulin polymerization, induced cell cycle arrest, and caused caspase-induced apoptosis in K562 cells. Additionally, compound 42 was significantly less cytotoxic in non-cancer cells compared to isoCA-4.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Review
Chemistry, Medicinal
Kena Zhang, Christine Tran, Mouad Alami, Abdallah Hamze, Olivier Provot
Summary: This review summarizes the synthesis and biological activities of pyrazino[1,2-a]indoles and pyrazino[1,2-a]indol-1-ones reported since 1997, as well as the discovery of biological activity of pyrazinoindole derivatives. The review discusses synthetic routes to access the pyrazinoindole unit and the properties of pyrazinoindoles, including neuropsychiatric, auto-immune, anti-infectious, and anti-cancer properties. It also covers the main accesses to pyrazinoindol-1-one substrates and the properties of pyrazinoindolones, such as anti-cancer, anti-infectious, anti-allergenic, and neuropsychiatric properties.
Article
Chemistry, Medicinal
Shannon Pecnard, Abdallah Hamze, Jerome Bignon, Bastien Prost, Alain Deroussent, Laura Gallego-Yerga, Rafael Pelaez, Ji Yeon Paik, Marc Diederich, Mouad Alami, Olivier Provot
Summary: In this study, various ligands related to Combretastatin A-4 and isoCombretastatin A-4 were designed, synthesized, and evaluated for their ability to inhibit tubulin polymerization. The lead compound 15d showed remarkable sub-nanomolar cytotoxicity against 9 human cancer cell lines, with an IC50 value below 1 nM.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Medicinal
Shannon Pecnard, Abdallah Hamze, Jean-Luc Pozzo, Mouad Alami, Olivier Provot
Summary: This review summarizes the various pathways to the oxazino[4,3-a]indole motif over the last decades. Representative examples illustrate the synthetic pathways and the biological activity of the synthesized oxazinoindoles will be mentioned whenever possible.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Review
Chemistry, Organic
Jun Yan, Jean-Luc Pozzo, Abdallah Hamze, Olivier Provot
Summary: Reactions for the deprotection of carbonyl derivatives have been a topic of interest in the scientific community. This comprehensive review provides an update to previous research, focusing on methods for the deprotection of thioacetals, thioketals, and oxathiolanes to their corresponding carbonyl compounds. Various approaches, such as the use of iodonium or bromonium ions, oxidants, photocatalysis, metal salts, or slightly acidic hydrolysis conditions, are discussed. Representative examples demonstrate the scope and tolerance of each protocol towards functional groups.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kena Zhang, Olivier Provot, Mouad Alami, Christine Tran, Abdallah Hamze
Summary: This study demonstrates the successful synthesis of various di- and tri-substituted alkenes with high chemoselectivity using N-tosylhydrazones and benzylic phosphates as electrophilic partners. The new catalytic system consisting of PdCl2(CH3CN)(2)/dppp, LiOtBu, and cyclopentyl methyl ether as the solvent exhibits good yields. Furthermore, gram-scale transformations and subsequent postfunctionalization of key intermediates are also reported in this study.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Romain Hany, Jean-Philippe Leyris, Guillaume Bret, Sylvie Mallie, Chamroeun Sar, Maxime Thouaye, Abdallah Hamze, Olivier Provot, Pierre Sokoloff, Jean Valmier, Pascal Villa, Didier Rognan
Summary: This study identifies small molecular weight ligands that can inhibit the Fms-like tyrosine kinase 3 (FLT3) receptor tyrosine kinase at the extracellular level. These ligands show strong inhibition in cell lines and a mouse model, demonstrating their potential as therapeutic inhibitors.
ACS CHEMICAL BIOLOGY
(2022)
Review
Biochemistry & Molecular Biology
Christine Tran, Abdallah Hamze
Summary: This review covers the recently published works on synthesizing highly functionalized imidazopyridines by light induction.
Review
Chemistry, Organic
Camille Hauguel, Jean-Luc Pozzo, Abdallah Hamze, Olivier Provot
Summary: This review summarizes the recent advances in the synthesis of pyrrolo[3,2-b]indoles, indolo[3,2-b]indoles, and their polycyclic counterparts through novel strategies using metal or non-metal salts. The review includes examples of functionalized compounds and discusses the properties and reaction mechanisms of selected heterocycles.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Christine Tran, Aicha Abdallah, Valentin Duchemann, Guillaume Lefevre, Abdallah Hamze
Summary: We developed a new approach for synthesizing substituted dihydrobenzo[c]carbazoles and indoles through iron-catalyzed hydrogen transfer reduction of nitroarenes followed by intramolecular cyclization. This strategy involves the use of a Knolker-type catalyst, Cs2CO3 as the base, and benzyl alcohol as the hydrogen donor. We synthesized 30 examples of aza-heterocycles with moderate to excellent yields using this approach. DFT calculations suggest an anionic mechanism for the reaction pathway.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Organic
Jun Yan, Christine Tran, Pascal Retailleau, Mouad Alami, Abdallah Hamze
Summary: Functionalized 4-aryl-4H-benzo[d][1,3]oxazines were synthesized using ortho-amide-N-tosylhydrazones under transition-metal-free conditions. This method utilizes readily available N-tosylhydrazones as the diazo compound precursors and involves an intramolecular ring closure reaction mediated by a protic polar additive (iPrOH), resulting in a wide range of functionalized oxazines in good to excellent yields. Additionally, the feasibility of this strategy was demonstrated by the gram-scale elaboration of a bromo-substituted 4H-benzo[d][1,3]oxazine and its post-functionalization through palladium-catalyzed cross-couplings.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Xinya Liu, Olivier Provot, Remi Franco, Pascal Retailleau, Mouad Alami, Vincent Gandon, Christine Tran, Abdallah Hamze
Summary: In this study, a methodology for synthesizing aza-heterocyclic compounds using N-tosylhydrazones as key reagents is presented. The main objective was to obtain six or seven-membered ring heterocycles, but the unexpected formation of bi-indole compounds in high yields was observed. Furthermore, the synthetic pathway allows for modifications at the C3 or C2 position of the indole, resulting in the formation of the respective 3'-phenyl-2'-biindole or carbazole derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Physical
Xinya Liu, Jean-Luc Pozzo, Abdallah Hamze, Mouad Alami, Olivier Provot
Summary: This article reviews the significance of water addition on unsymmetrical internal alkynes in organic chemistry and presents a range of highly regioselective methods for different types of internal alkynes. It discusses hydration reactions of electron-rich and -poor diarylalkynes, arylalkylalkynes, and internal alkynes directed by carbonyl groups. The article also examines hydration reactions involving alkynes linked to CF3, esters, ketones, and heteroatoms. Mechanistic hypotheses explaining the regioselectivity in hydration reactions are discussed.
Article
Chemistry, Organic
Kena Zhang, Olivier Provot, Christine Tran, Mouad Alami, Abdallah Hamze
Summary: A new methodology for synthesizing sulfonyl-N-phenylaniline derivatives by trapping bromo-sulfone derivatives with amines generated from N-tosylhydrazones (NTHs) was described. The reaction was successful for a wide range of NTHs and amines, and tolerated various functional groups on both coupling partners (35 examples). Mechanistic studies showed that sulfone formation did not proceed through a radical pathway.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Chemistry, Organic
Yunxin Yao, Mouad Alami, Abdallah Hamze, Olivier Provot
Summary: Research on new synthetic pathways to access the pyrido[1,2-a]indole unit found in various organic compounds has intensified in recent years. This review categorizes the synthesis of pyrido[1,2-a]indoles into two parts, based on whether metal catalysis is used or not.
ORGANIC & BIOMOLECULAR 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)
