Article
Multidisciplinary Sciences
Zhe Chang, Jialin Huang, Si Wang, Geshuyi Chen, Heng Zhao, Rui Wang, Depeng Zhao
Summary: Late-stage C(sp(3))-H bond functionalization of N-heterocycles with broad substrate scope remains a challenge in modern chemical synthesis and pharmaceutical chemistry, but here the authors demonstrate copper-catalysed late-stage C(sp(3))-H functionalization of N-heterocycles using commercially available catalysts under mild reaction conditions. The approach shows potential utility in modifying medicinally important skeletons with a range of nucleophiles.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Hao Deng, Marco Bengsch, Nico Tchorz, Constanze N. Neumann
Summary: This article introduces a novel method for fine-tuning phosphine ligands, which enables diversification of phosphine compounds by introducing different substituents into previously inaccessible positions. Compared to existing methods, this approach overcomes the limitations of phosphorus-directed reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Mirxan Farizyan, Rita de Jesus, Jyotirmoy Dey, Manuel van Gemmeren
Summary: Aryl iodides are important in organic chemistry due to their versatility in metal-mediated cross-coupling reactions. This study describes a sterically controlled iodination of arenes through an isodesmic C-H/C-I bond metathesis approach using dual ligand-based catalysts for arene-limited nondirected C-H activation. The protocol offers a complementary product spectrum to traditional methods and shows broad applicability and suitability for late-stage modification.
Article
Chemistry, Multidisciplinary
Arup Mondal, Manuel van Gemmeren
Summary: Alkynes are important motifs in organic synthesis due to their presence in natural products and bioactive molecules. The method of inserting alkynes into (hetero)arenes relies heavily on the regioselectivity of the halogenation step, and can achieve selective alkynylation of thiophenes. The developed palladium-catalyzed C-H activation/alkynylation of thiophenes allows for regiodivergent reactions and late-stage modifications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Zhijun Zuo, Armido Studer
Summary: In this study, a photoredox-catalyzed 1,3-oxyalkynylation reaction of cyclopropanes with EBXs was described, offering a wide substrate scope.
Article
Chemistry, Organic
Lin Ma, Xiaohui Zhang, Yanyan Tuo, Qing-Zhong Zheng
Summary: An efficient Cp*Rh(III)-catalyzed regioselective C(sp(2))-H mono- and dialkynylation of thioamides was described. This reaction was performed under mild conditions with high yields, demonstrating versatility by controlled mono- and dialkynylation. The application of this approach in late-stage functionalization of two drug molecules (Adapalene and Amoxapine) was also demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Akanksha Singh Baghel, Ramendra Pratap, Amit Kumar
Summary: In this study, a simple and efficient catalytic system for the dialkynylation of aromatic/heteroaromatic ketones via double C-H bond activation is reported. The weakly and native carbonyl group is used as the desired directing group, and a less expensive ruthenium(II)-salt is employed as the catalyst. The developed protocol demonstrates high compatibility, tolerance, and sustainability towards various functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Li Zhang, Tobias Ritter
Summary: Aromatic C-H late-stage functionalization poses challenges in terms of reactivity, selectivity, and substrate scope, but also shows potential for development. It is necessary to address current challenges and explore new strategies and directions for growth.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Ashfaq Ahmad, Himangsu Sekhar Dutta, Mohit Kumar, Raziullah, Manoj Kumar Gangwar, Dipankar Koley
Summary: A palladium catalyzed directing group assisted cross-coupling reaction has been developed for the synthesis of β-arylethylamine derivatives. The method is applicable to a wide range of substrates and can tolerate the presence of various external additives.
Article
Chemistry, Multidisciplinary
Eric Tan, Marc Montesinos-Magraner, Cristina Garcia-Morales, Joan Guillem Mayans, Antonio M. Echavarren
Summary: The ortho-alkynylation of nitro-(hetero)arenes occurs in the presence of a Rh(iii) catalyst, leading to the regioselective formation of various alkynylated nitroarenes. These products can be further modified through selective reduction of the nitro group or palladium-catalysed couplings. Experimental and computational mechanistic studies indicate that the reaction proceeds through a turnover-limiting electrophilic C-H metalation ortho to the strongly electron-withdrawing nitro group.
Article
Multidisciplinary Sciences
Peng Wang, Jiang Liu, Xiaomei Zhu, Zhengqing Kenry, Zhengqing Yan, Jiahui Yan, Jitong Jiang, Manlin Fu, Jingyan Ge, Qing Zhu, Yuguo Zheng
Summary: Cyclic peptides have attracted attention in the pharmaceutical industry, but there are limited methods for their synthesis. This study presents an efficient and direct method for peptide cyclization using rhodium(III)-catalyzed C(7)-H maleimidation. The resulting cyclic peptides exhibit higher bioactivity and can be used for creating peptide-drug conjugates.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Akanksha Singh Baghel, Amit Kumar
Summary: In this study, we developed a ruthenium(ii)-catalyzed weakly coordinating primary amide-assisted ortho-di-alkynylation of (hetero)arylamides via double C-H bond activation using bromo-alkynes as coupling partners. The strategy demonstrated attractive features including the use of inexpensive ruthenium(ii)-salt, external auxiliary-free directing group, simple reaction conditions, broad substrate scope, high reaction yields, and scalability of the synthesis.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Carlos Santiago, Hao Chen, Arup Mondal, Manuel van Gemmeren
Summary: In this study, dual ligand-based palladium catalysts were used for late-stage olefination of arenes, successfully functionalizing complex arene substrates. The method utilizes the arene as a limiting reactant and controls the regioselectivity of the transformation by the steric and electronic properties of the substrate, providing a new pathway for preparing regioisomers.
Article
Chemistry, Multidisciplinary
Christian Schnepel, Veronica I. Dodero, Norbert Sewald
Summary: A biocatalytic approach was developed to selectively functionalize indigo derivatives, providing a modular platform for novel compounds with attractive spectral properties. This method not only improves yields but also allows for the synthesis of a small set of 6,6'-diarylindigo derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Weiliang Yuan, Xiaojiao Li, Zisong Qi, Xingwei Li
Summary: A palladium-catalyzed method for the synthesis of 3-acyl and -allyl indoles has been developed, utilizing nucleophilic cyclization of ortho-alkynylanilines and ring opening of three-membered rings. The functionalized indoles were obtained in good yields and high stereoselectivity, providing an alternative approach under mild and redox-neutral conditions.
Article
Chemistry, Multidisciplinary
Kiron Kumar Ghosh, Alexander Uttry, Arup Mondal, Francesca Ghiringhelli, Philipp Wedi, Manuel van Gemmeren
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Review
Chemistry, Organic
Hao Chen, Mirxan Farizyan, Manuel van Gemmeren
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Review
Chemistry, Organic
Johannes E. Erchinger, Manuel van Gemmeren
Summary: This article discusses the combination of electrochemistry and Pd-catalyzed C-H activation/functionalization to achieve C-C, C-X, C-O, and C-P bond formation.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Arup Mondal, Manuel van Gemmeren
Summary: Alkynes are important motifs in organic synthesis due to their presence in natural products and bioactive molecules. The method of inserting alkynes into (hetero)arenes relies heavily on the regioselectivity of the halogenation step, and can achieve selective alkynylation of thiophenes. The developed palladium-catalyzed C-H activation/alkynylation of thiophenes allows for regiodivergent reactions and late-stage modifications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Francesca Ghiringhelli, Alexander Uttry, Kiron Kumar Ghosh, Manuel Van Gemmeren
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Editorial Material
Chemistry, Multidisciplinary
Sabine Bognar, Manuel van Gemmeren
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Sabine Bognar, Manuel van Gemmeren
Summary: A synthetically simple general one-step protocol was developed for the selective synthesis of a broad range of unsymmetrical dithioacetals consisting of one aromatic and one aliphatic thiol moiety. The mixed S,S-acetals were obtained in high yields, demonstrating excellent selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Philipp Wedi, Mirxan Farizyan, Klaus Bergander, Christian Mueck-Lichtenfeld, Manuel van Gemmeren
Summary: Recent discovery of palladium catalysts has enabled direct-group-free C-H activation of arenes without excess substrate, allowing for late-stage modification of complex organic molecules. The success lies in the use of two complementary ligands, N-acyl amino acid and N-heterocycle. Mechanistic studies have identified catalytically active species and a transition state model that explains the exceptional activity and selectivity of these catalysts, with potential for further method development.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Alexander Uttry, Sourjya Mal, Manuel van Gemmeren
Summary: The study describes the late-stage deuteration of free carboxylic acids and enables the functionalization of non-activated methylene beta-C(sp(3))-H bonds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Mirxan Farizyan, Arup Mondal, Sourjya Mal, Fritz Deufel, Manuel van Gemmeren
Summary: The study presents a palladium-catalyzed late-stage deuteration of arenes using D2O as a deuterium source and N,N-bidentate ligands with N-acylsulfonamide group. The protocol allows for high degrees of deuterium incorporation with exceptional functional group tolerance, enabling the deuteration of complex substrates. This method is expected to be useful for drug development processes and mechanistic studies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Arup Mondal, Manuel van Gemmeren
Summary: This Review compares silver-based and silver-free methods for carbon-hydrogen activation and focuses on strategic approaches to develop silver-free C-H activation, providing the means for the development of sustainable methods for C-H activation to the readers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Carlos Santiago, Hao Chen, Arup Mondal, Manuel van Gemmeren
Summary: In this study, dual ligand-based palladium catalysts were used for late-stage olefination of arenes, successfully functionalizing complex arene substrates. The method utilizes the arene as a limiting reactant and controls the regioselectivity of the transformation by the steric and electronic properties of the substrate, providing a new pathway for preparing regioisomers.
Article
Chemistry, Organic
Manuel van Gemmeren, Benjamin List
Summary: This article details the development of Select Crowd Reviewing from the initial idea through a pilot phase to its current status as the default method for evaluating manuscripts at Synlett and SynOpen. The workflow for manuscript evaluation using Select Crowd Reviewing is described, along with a discussion of the advantages it offers compared to traditional peer review.