Article
Chemistry, Multidisciplinary
Jun Chen, Yu-Jie Liang, Peng-Zi Wang, Guo-Qing Li, Bin Zhang, Hao Qian, Xiao-Die Huan, Wei Guan, Wen-Jing Xiao, Jia-Rong Chen
Summary: This study presents a photoinduced copper-catalyzed cross-coupling reaction for the generation of allylic esters. The reaction proceeds at room temperature with high regio- and enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Toru Hashimoto, Keisuke Shiota, Kei Funatsu, Yoshitaka Yamaguchi
Summary: A nickel-catalyzed cross-coupling reaction between aryl halides and primary or secondary aliphatic alcohols has been achieved using a bench-stable nickel complex supported by a monoanionic O,N,N-tridentate ligand. The reaction proceeds smoothly without the need for a phosphine ligand, giving moderate to good yields of alkyl aryl ethers.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Ying Lin, Liang Zou, Renren Bai, Xiang-Yang Ye, Tian Xie, Yang Ye
Summary: We present an easy and efficient method for vinylation using Fe-catalyzed cross-electrophile coupling of readily available vinyl- and hydro-chlorosilanes with a range of substituted alkenyl bromides using manganese as the terminal reductant. This modular approach allows the formation of various vinyl orgaonosilanes, including electron-rich, electron-poor, and ortho-/meta-/para-substituted vinyl electrophiles, with excellent functional group tolerance and broad substrate scope. Furthermore, this method successfully modified substrates with structurally complex natural products and pharmaceutical motifs, demonstrating its potential in gram-scale reactions and derivatization.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Garrett P. R. Freure, Eric A. Skrotzki, Jean-Danick E. Lavertu, Stephen G. Newman
Summary: Various methods have been investigated recently for the arylation of weakly acidic C(sp(3))-H bonds, with this study focusing on a base-mediated approach using organometallic superbases. The study developed conditions for high selectivity metalation using either n-BuLi/diamine or n-BuLi/KOtBu superbases, allowing for direct use in cross-coupling or formation of organozincs for reactions with functional groupdense organohalides.
Article
Chemistry, Organic
Rhys A. Lippa, David J. Battersby, John A. Murphy, Tim N. Barrett
Summary: The synthesis of substituted arylethylamines via palladium-catalyzed coupling between (chloromethyl)aryls and N,N-dialkylaminomethyltrifluoroborate salts was reported in this study. Rapid hit identification was achieved using microscale high-throughput experimentation, followed by millimolar-scale reaction parameter optimization. A range of structurally and electronically varied arylethylamine products were obtained in moderate to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Avishek Das, Nitin T. Patil
Summary: A ligand-enabled gold-catalyzed C(sp2)-O cross-coupling reaction between aryl iodides and aliphatic alcohols is reported. The method is demonstrated to be useful for the synthesis of various aryl alkyl ethers, including complex biomolecules and medicinally relevant motifs. The importance of gold catalysis is highlighted in overcoming selectivity issues observed with other transition metal catalysts in C-O cross -coupling reactions.
Article
Chemistry, Physical
Avishek Das, Nitin T. Patil
Summary: Reported in this study is a ligand-enabled gold-catalyzed C(sp2)-O cross-coupling reaction between aryl iodides and aliphatic alcohols. The usefulness of the method is demonstrated by successfully synthesizing a variety of aryl alkyl ethers, including complex biomolecules and medicinally relevant motifs. The importance of gold catalysis is highlighted by overcoming the selectivity issues commonly observed when other transition metals are used as catalysts for C-O cross-coupling reactions.
Review
Chemistry, Multidisciplinary
Massimo C. D'Alterio, Eric Casals-Cruanas, Nikolaos V. Tzouras, Giovanni Talarico, Steven P. Nolan, Albert Poater
Summary: The story of C-C bond formation involves various reactions, with Suzuki-Miyaura reaction being one of the most outstanding ones. The focus is on the formation of catalytically active species, with preactivation potentially playing a role as the rate determining step in the overall reaction. Computational chemistry plays a key role in identifying the rate determining step and achieving milder conditions in experimental settings through predictive catalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Igor Beckers, Besir Krasniqi, Prashant Kumar, Daniel Escudero, Dirk De Vos
Summary: Two indoles linked by a C-C bond have emerged as promising scaffolds in medicinal chemistry. In this study, selective C-H/C-H cross-coupling of N-substituted indoles without directing groups was achieved under mild conditions, driven by molecular oxygen. The ligand-controlled selectivity can be exploited to achieve selective cross-coupling between two indoles with different substitution patterns.
Article
Chemistry, Multidisciplinary
Yaxin Zeng, Hui Yang, Jiayi Du, Qin Huang, Guoliang Huang, Ying Xia
Summary: The control of linear/branched selectivity in transition-metal catalyzed allyl-allyl cross-coupling reactions has been investigated in this study. It has been found that the terminal/internal regioselectivity can be switched by fine-tuning the rhodium catalytic system. Different types of 1,5-dienes are produced with good yields, exhibiting isomerized terminal, internal, and terminal regioselectivity.
Article
Chemistry, Organic
Joseph Becica, David C. Leitch
Summary: Palladium catalysis can provide new oxygenate-based feedstocks and building blocks by activating strong C-O bonds, demonstrating not only difficult C-O oxidative additions but also Suzuki-type cross-couplings of alkenyl carboxylates under mild conditions. Depending on the reaction conditions, either a typical Pd(0)/(II) mechanism or a redox-neutral Pd(II)-only mechanism can operate, with C-C bond formation occurring through carbopalladation of the alkene, and C-O cleavage by beta-carboxyl elimination in the latter pathway.
Article
Chemistry, Organic
Mengting Kou, Ziqiang Wei, Zhen Li, Bin Xu
Summary: A copper-catalyzed sulfinyl cross-coupling reaction of sulfinamides with aldehyde-derived N-tosylhydrazones is reported. This approach provides an efficient and novel way to construct structurally diverse sulfoxides, with broad substrate scope and compatibility with various functional groups and pharmacophores. Moreover, the reaction can be scaled up to gram scale and carried out in a one-pot fashion directly from aldehydes.
Article
Chemistry, Applied
Anastasia Hager, Nicolas Guimond, Lars Grunenberg, Christine Hanisch, Sebastian Steiger, Andre Preuss
Summary: The traditional synthesis method of the androgen receptor antagonist BAY 1161116 was inefficient and difficult, while a new synthetic pathway using trans-aminocyclohexanol and a palladium-catalyzed etherification reaction showed improved scalability and efficiency. This four-step synthesis can be reliably conducted on a multikilogram scale, with purification achieved through simple extraction and crystallization procedures.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Chemistry, Multidisciplinary
Dejiang Zhang, Liyuan Le, Renhua Qiu, Wai-Yeung Wong, Nobuaki Kambe
Summary: A strategy for the formation of antimony-carbon bond via nickel-catalyzed cross-coupling of halostibines was developed. This method has a wide substrate scope and is compatible with various functional groups. The successful synthesis of arylated stibine demonstrated the high synthetic potential of this transformation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yong-Feng Cheng, Zhang-Long Yu, Yu Tian, Ji-Ren Liu, Han-Tao Wen, Na-Chuan Jiang, Jun-Qian Bian, Guo-Xiong Xu, Dan-Tong Xu, Zhong-Liang Li, Qiang-Shuai Gu, Xin Hong, Xin-Yuan Liu
Summary: The transition-metal-catalysed cross-coupling reaction has been widely used to construct carbon-carbon/heteroatom bonds. However, the development of heteroatom-heteroatom cross-couplings has been challenging. In this study, a new strategy using single-electron reductive elimination under Cu catalysis was demonstrated for enantioselective S-O coupling. This reaction showed its synthetic potential in preparing chiral alcohols, utilizing biomass-derived feedstock glycerol, and catalytic 4,6-desymmetrization of inositol. These results highlight the potential of enantioselective radical heteroatomic cross-coupling as a general chiral heteroatom-heteroatom bond formation strategy.
Article
Chemistry, Multidisciplinary
Aaron J. Mallek, Bradley L. Pentelute, Stephen L. Buchwald
Summary: This study discusses the selective N-arylation of p-aminophenylalanine in polypeptides using pre-formed palladium oxidative addition complexes, enabling chemoselective C-N bond formation on peptides containing multiple other amino groups. By utilizing palladium complexes derived from electron-poor aryl halides, p-aminophenylalanine can be fully arylated at micromolar concentrations in aqueous buffer in a short amount of time. A complementary protocol using the non-nucleophilic, organic base 1,5-diazabicyclo(4.3.0)non-5-ene (DBN) expands the substrate scope and provides high conversion rates of up to 97%.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Muhammad Jbara, Sebastian Pomplun, Carly K. Schissel, Susana Wilson Hawken, Ann Boija, Isaac Klein, Jacob Rodriguez, Stephen L. Buchwald, Bradley L. Pentelute
Summary: Novel synthetic TF mimetics have been developed to inhibit oncogenic Myc-driven transcription by antagonistic DNA-binding, leading to reduced cancer cell proliferation. The use of flow chemistry and palladium(II) OACs offers a practical strategy to generate bioactive compounds for inhibiting tumor cell proliferation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Ryan P. King, Shane W. Krska, Stephen L. Buchwald
Summary: Palladium oxidative addition complexes (OACs) have emerged as useful tools for challenging bond connections, but each complex can only be formed with one dative ligand at a time. A ligand exchange protocol has been developed to prepare a series of OACs with various ancillary ligands from a common complex, which have been further applied to cross-coupling transformations.
Article
Chemistry, Organic
Ryan P. King, Shane W. Krska, Stephen L. Buchwald
Summary: The utilization of isolated Palladium Oxidative Addition Complexes (OACs) has been crucial for Pd-catalyzed and Pd-mediated cross-coupling reactions. However, the instability of their precursor complexes has limited their widespread utility. By using Campora's palladacycle as a stable precursor, a series of biarylphosphine ligated OACs were prepared, including those with pharmaceutical-derived aryl halides, showing relevance to bioconjugation research.
Article
Chemistry, Multidisciplinary
Sheng Feng, Yuyang Dong, Stephen L. Buchwald
Summary: In this study, an alternative method for the asymmetric hydroaminocarbonylation of olefins using dual copper hydride and palladium catalysis was described. This method enables the synthesis of enantioenriched amides using readily available carbamoyl chlorides as the carbamoylating reagent, and is applicable to various types of olefins with good yields and excellent enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Correction
Chemistry, Multidisciplinary
Martin Gazvoda, Heemal H. Dhanjee, Jacob Rodriguez, Joseph S. Brown, Charlotte E. Farquhar, Nicholas L. Truex, Andrei Loas, Stephen L. Buchwald, Bradley L. Pentelute
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yuyang Dong, Alexander W. Schuppe, Binh Khanh Mai, Peng Liu, Stephen L. Buchwald
Summary: This article introduces a CuH-catalyzed selective reductive coupling reaction of vinyl heteroarenes with aldehydes and ketones. The selectivity of the reaction is controlled by the choice of the ancillary ligand. This method shows excellent selectivity, tolerates various functional groups and heterocycles, and provides a direct route to functionalized saturated heterocyclic structures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Martin Gazvoda, Heemal H. Dhanjee, Jacob Rodriguez, Joseph S. Brown, Charlotte E. Farquhar, Nicholas L. Truex, Andrei Loas, Stephen L. Buchwald, Bradley L. Pentelute
Summary: This article describes a method for embedding carborane moieties into small molecules, peptides, and proteins. The strategy involves palladium-mediated C-X bond formation and enables selective conjugation of carborane-containing groups with other molecules in aqueous buffer. The method has been successfully applied to nanobodies, fully synthetic affibodies, and antibody therapeutics such as Herceptin and Cetuximab.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yuyang Dong, Kwangmin Shin, Binh Khanh Mai, Peng Liu, Stephen L. Buchwald
Summary: This paper reports an asymmetric olefin hydromethylation protocol enabled by CuH catalysis, in which methyl tosylate is used as a methyl source and iodide ion converts it into the active reactant methyl iodide. The method demonstrates broad applicability and tolerance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Elaine C. Reichert, Kaibo Feng, Aaron C. Sather, Stephen L. Buchwald
Summary: We report a versatile method for the Pd-catalyzed C-N cross-coupling of heteroaryl halides with primary and secondary amines, achieving good-to-excellent yields. The use of a specific base and a supported Pd catalyst enables the coupling of challenging heteroarenes and sterically demanding amines. This method has broad applicability and allows the synthesis of densely functionalized medicinal chemistry building blocks.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yuxuan Ye, Seoung-Tae Kim, Ryan P. King, Mu-Hyun Baik, Stephen L. Buchwald
Summary: Pd-catalyzed nucleophilic fluorination reactions are important for the synthesis of fluoroarenes and fluoroalkenes. However, the regioselectivity of these reactions is often poor, generating a mixture of difficult-to-separate regioisomeric products. In this study, the addition of a substoichiometric quantity of TESCF3 significantly improved the regioselectivity by diminishing the formation of LPd-cyclohexyne complexes through an unexpected dearomatization pathway involving nucleophilic attack from a trifluoromethyl anion (CF3-).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Seoung-Tae Kim, Michael J. Strauss, Albert Cabre, Stephen L. Buchwald
Summary: A new class of anionic ligands for Cu-catalyzed C-N couplings has been developed, which enables efficient amination of aryl bromides under mild conditions. This ligand design increases the electron density on Cu and stabilizes the active anionic CuI complex, leading to enhanced reactivity and a broad substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Simon L. Rossler, Nathalie M. Grob, Stephen L. Buchwald, Bradley L. Pentelute
Summary: This study establishes abiotic peptides as carriers of information for the encoding of small-molecule synthesis. These peptides are used to encode diverse small-molecule synthesis and successfully discover protein ligands. This work demonstrates the potential for abiotic peptides in accelerating the discovery of therapeutic targets.
Article
Chemistry, Multidisciplinary
Dennis A. Kutateladze, Binh Khanh Mai, Yuyang Dong, Yu Zhang, Peng Liu, Stephen L. Buchwald
Summary: A copper hydride-catalyzed approach has been developed for the synthesis of Z-configured trisubstituted alkenes with high stereo- and regioselectivity. This method provides a valuable strategy for accessing challenging classes of alkenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Anthony J. Rojas, Justin M. Wolfe, Heemal H. Dhanjee, Ivan Buslov, Nicholas L. Truex, Richard Y. Liu, Walter Massefski, Bradley L. Pentelute, Stephen L. Buchwald
Summary: The synthesis of palladium oxidative addition complexes derived from unprotected peptides is described. These complexes can react with thiols in aqueous buffer, providing an efficient method for bioconjugation. Using this strategy, peptides can be functionalized with small molecules to prepare modified aryl thioether side-chains at low micromolar concentrations. Additionally, peptide-peptide and peptide-protein ligations are demonstrated under dilute aqueous conditions.
