Article
Chemistry, Physical
Jiamin Huang, Feixiang Sun, Weiping Liu
Summary: In this study, the deoxygenation of secondary and tertiary amides using [Mn(CO)5Br] with Ph2SiH2 or inexpensive PMHS as reducing agents was reported, providing a convenient method for the synthesis of corresponding secondary and tertiary amines. The transformation is operationally simple, proceeds under mild conditions without external ligands, and exhibits high catalytic efficacy and good functional-group tolerance. Furthermore, the generality of this catalytic system was demonstrated by the late-stage modification of bioactive molecules.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Md Jabed Hossain, Brij Kumar Shah, Shabana Khan
Summary: In this study, a convenient method for the synthesis of amines using accessible Ce[N(SiMe3)(2)](3)(THF)(3) catalyst under mild conditions was developed. The reduction of 1 degrees and 2 degrees amides to amines was achieved with high yields. This methodology was also successfully applied for the synthesis of indole derivatives.
Article
Chemistry, Organic
Christiana Bockisch, Edward D. Lorance, Hilairy E. Hartnett, Everett L. Shock, Ian R. Gould
Summary: Hydrothermal dehydration is an attractive method for deoxygenation and upgrading of biofuels, particularly for mono-alcohols. However, polyols are more challenging to deoxygenate and have more complex reaction pathways, with the interactions between hydroxyl groups influencing the reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Federico Verdicchio, Agustin Galindo
Summary: The molybdenum-catalysed deoxydehydration (DODH) of vicinal diols to alkenes was investigated using density functional theory (DFT). The mechanism of DODH was studied using a phosphane as a reductant and a [Mo(O)(2)(Q(R))(2)] complex as a catalyst. Two alternative routes, A and B, were analyzed, and it was found that pathway B, where the reduction by phosphane preceded the diol condensation, was energetically preferred.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Kun Zhao, Shan Yang, Qi Gong, Longhui Duan, Zhenhua Gu
Summary: A Cu-catalyzed enantioselective ring-opening alkoxygenation reaction of cyclic diaryliodonium salts and diols was reported, with borinic acids playing a key role in selectively activating different types of diols. The proposed catalytic cycle involves a key ion pair model to account for the observed enantioselectivity. This study provides insights into the design of chiral catalysts for selective synthesis of cyclic molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
William C. Spaller, Jennifer Q. Lu, Benjamin J. Stokes
Summary: In this study, a palladium-catalyzed deoxygenative transfer hydrogenation of ketones using B-2(OH)(4) as the sole additive was described. Deuterium labeling experiments with B-2(OD)(4) revealed that the incorporated protons exclusively originated from the diboron reagent. Spectroscopic evidence indicated the presence of a borate ester intermediate. This approach can be applied to deoxygenate various aromatic ketones.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Oliver P. Williams, Alyah F. Chmiel, Myriam Mikhael, Desiree M. Bates, Charles S. Yeung, Zachary K. Wickens
Summary: In this study, a practical protocol for removing alcohol functional groups through reductive cleavage of their benzoate ester analogs is described. The transformation requires a strong single electron transfer (SET) reductant and a method to accelerate slow fragmentation after substrate reduction. A photocatalytic system was developed to generate a potent reductant from formate salts with Bronsted or Lewis acids that promote fragmentation. This deoxygenation procedure is effective for diverse alcohols and enables various transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
J. Armando Lujan-Montelongo, Jeferson B. Mateus-Ruiz, Ricardo M. Valdez-Garcia
Summary: This review presents a comprehensive analysis of the strategies and methodologies for reducing C-O and heteroatomic-oxygen bonds (N-O, S-O, P-O) using I-2/I-, as well as other synthetically relevant bonds such as C-C, N-N, C-N, C-X, C-S. It focuses on discussing the mechanistic details provided by the original authors and also includes examples of using other halides (Br and Cl) as reductants.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Engineering, Environmental
Yeonjoon Kim, Mohammed A. Jabed, David M. Price, Dmitri Kilin, Seonah Kim
Summary: This study provides rational design guidelines for supported V2O5 catalysts in the catalytic upgrading of lignocellulosic biomass, particularly in the conversion of guaiacol to phenol. The tilt angle of the aryl group in the hydrogen migration transition state is identified as a key descriptor in determining the catalytic activity of phenol formation.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Lifeng Sun, Pradeep Chopra, Geert-Jan Boons
Summary: A new method for the synthesis of heparan sulfate oligosaccharides composed of unsulfonated fragments of different lengths was reported. Competition binding studies showed that the length of the unsulfonated fragment modulates the binding of chemokines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Na Shao, Valerie Monnier, Laurence Charles, Jean Rodriguez, Cyril Bressy, Adrien Quintard
Summary: This study reports a multicatalytic strategy for the synthesis of a new type of scaffold containing a tetrasubstituted stereocenter embedded in fluorohydrin motifs. The method involves organocatalyzed fluorination and diastereoselective aldol reaction, resulting in the stereoselective synthesis of fluorinated 1,3-diols.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Pei-Sen Gao, Chang-Wang Pan, Cheng Liu, Wen -Tong Chen
Summary: Asymmetric electrocatalysis offers a unique approach to obtain enantioenriched molecules that are difficult to obtain through conventional methods. This study developed a novel bifunctional electrocatalyst, enabling the oxidative kinetic resolution of chiral 1,4-diols and gamma-lactones. The work demonstrates the potential of bifunctional electrocatalysis for asymmetric synthetic methods and its importance in the development of novel electrocatalytic methods.
MOLECULAR CATALYSIS
(2024)
Article
Chemistry, Multidisciplinary
Yu Zhanglong, Li Zhongliang, Yang Changjiang, Gu Qiangshuai, Liu Xinyuan
Summary: This review summarizes the research progress in copper-catalyzed enantioselective desymmetrization of diols, and provides a brief perspective on its application prospects in medicinal chemistry, total synthesis, and materials science.
ACTA CHIMICA SINICA
(2023)
Article
Chemistry, Multidisciplinary
Christian J. Oswood, David W. C. MacMillan
Summary: Traditional approaches to stereoselective synthesis usually require high levels of control in forming new stereocenters. This study presents an alternative method where the stereochemistry of organic substrates is selectively edited without further structural modification, allowing access to rare or valuable stereochemical configurations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Thaddaeus Thorwart, Daniel Roth, Lutz Greb
Summary: The article introduces a novel per(trifluoromethyl)catechol silicon complex, which exhibits strong Lewis acidity and can catalyze deoxygenations of aldehydes, ketones, and amides. This compound represents one of the strongest neutral Lewis acids accessible in the condensed phase.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Yong Ho Lee, Elliott H. Denton, Bill Morandi
Summary: Hydroformylation is a crucial catalytic reaction in synthesis, and developing carboformylation reactions has the potential to rapidly increase molecular complexity in valuable aldehyde synthesis. Overcoming the challenges of direct carboformylation reactions with a palladium-catalyzed strategy offers creative opportunities in carbonylation chemistry.
Article
Chemistry, Organic
Eric Falk, Valentina C. M. Gasser, Bill Morandi
Summary: A newly developed, highly electrophilic aminating reagent enables the direct synthesis of unprotected N-methylanilines from simple arenes, displaying broad functional group tolerance under mild reaction conditions. Catalytic amounts of a benign iron salt are employed in the reactions.
Article
Multidisciplinary Sciences
Xichang Dong, Johannes L. Roeckl, Siegfried R. Waldvogel, Bill Morandi
Summary: The study presents an electrochemically assisted shuttle (e-shuttle) paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, which can be used to synthesize dihalogenated molecules or recycle waste materials. The method demonstrates dibromination or dichlorination of alkenes using simple setup with inexpensive graphite electrodes. Additionally, it shows the complete dechlorination of hexachlorinated lindane to benzene using simple alkene acceptors in soil samples.
Article
Chemistry, Multidisciplinary
Philip Boehm, Tristano Martini, Yong Ho Lee, Bastien Cacherat, Bill Morandi
Summary: An efficient palladium-catalyzed iodination method has been developed for the synthesis of iodides from inexpensive and abundant aryl and vinyl carboxylic acids, including complex drug-like scaffolds. The unique mechanism involves C-P reductive elimination to form Xantphos phosphonium chloride, which then initiates an unusual halogen exchange by outer sphere nucleophilic substitution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Marius D. R. Lutz, Valentina C. M. Gasser, Bill Morandi
Summary: The development of transfer hydrogenation and borrowing hydrogen reactions has allowed for new possibilities in manipulating simple alcohols, while transfer hydrocarbylation can increase the versatility of tertiary alcohols. A novel catalytic method was reported for transfer hydrocarbylation, which involves a redox-neutral beta-carbon elimination mechanism. The experimental evidence supports the feasibility of this method for manipulating tertiary alcohols in catalysis.
Article
Chemistry, Multidisciplinary
Sayanti Chatterjee, Ingolf Harden, Giovanni Bistoni, Rebeca G. Castillo, Sonia Chabbra, Maurice van Gastel, Alexander Schnegg, Eckhard Bill, James A. Birrell, Bill Morandi, Frank Neese, Serena DeBeer
Summary: In this study, a mechanism of iron-catalyzed direct synthesis of unprotected aminoethers from olefins using a hydroxyl amine derived reagent was investigated through various analytical and spectroscopic techniques along with high-level quantum chemical calculations. The use of iron-coordinated nitrogen-centered radicals as reactive intermediates in catalysis was demonstrated to be potential and important.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Julia C. Reisenbauer, Benjamin N. Bhawal, Nicola Jelmini, Bill Morandi
Summary: This article reports a method for hydrocyanation reactions of alkenes and alkynes using commercially available aliphatic nitriles as a substitute for toxic hydrogen cyanide (HCN). The reaction employs a catalytic amount of inexpensive and stable NiCl2 along with a cocatalyst. The scalability and robustness of this method have been demonstrated.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Multidisciplinary
Ori Green, Patrick Finkelstein, Miguel A. Rivero-Crespo, Marius D. R. Lutz, Michael K. Bogdos, Michael Burger, Jean-Christophe Leroux, Bill Morandi
Summary: This study introduces a unique class of selective fluorescent carbon dioxide sensors that address the challenge of selective sensing at the molecular level. The sensors demonstrate utility in various multidisciplinary applications, showcasing their potential as broadly applicable tools to monitor and visualize carbon dioxide.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Tristan Delcaillau, Hendrik L. Schmitt, Philip Boehm, Eric Falk, Bill Morandi
Summary: The intramolecular carbothiolation of unsaturated hydrocarbons using a palladium-NHC catalyst was reported. The reaction showed excellent tolerance and chemoselectivity, and could be applied to the synthesis of various sulfur-containing compounds.
Article
Chemistry, Physical
Georgios Toupalas, Bill Morandi
Summary: This study presents a strategy to eliminate the need for an exogenous base in catalytic reactions by using non-innocent electrophiles (NIE) equipped with a masked base that is released during the reaction. The universal applicability of this strategy was demonstrated by converting multiple base-dependent reactions into base-free homogeneous processes, and the advantageous features of NIEs were showcased in various applications.
Article
Chemistry, Multidisciplinary
Philip Boehm, Patrick Mueller, Patrick Finkelstein, Miguel A. Rivero-Crespo, Marc-Olivier Ebert, Nils Trapp, Bill Morandi
Summary: Functional group metathesis is an emerging field in organic chemistry with promising synthetic applications. This study provides a detailed mechanistic understanding of the nickel-catalyzed functional group metathesis reaction between aryl methyl sulfides and aryl nitriles, combining experimental and computational results. The findings support an alternative mechanism involving a key transmetalation step and offer insights for improving the catalytic protocol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Georgios Toupalas, Gianin Thomann, Lukas Schlemper, Miguel A. Rivero-Crespo, Hendrik L. Schmitt, Bill Morandi
Summary: We report a direct arylation reaction that utilizes non-innocent isoureas to further polarize the C-O bond and enable catalytic turnover under exogenous base-free conditions. The developed concept allows for the formation of a C-C bond between differently decorated coupling partners and provides high orthogonality over conventional electrophiles. Additionally, the preformed isoureas can be leveraged for rapid, exogenous base-free coupling reactions under conventional thermal conditions.
Article
Multidisciplinary Sciences
Julia C. Reisenbauer, Ori Green, Allegra Franchino, Patrick Finkelstein, Bill Morandi
Summary: Reliable strategies for directly editing the core skeleton of pharmaceutical lead compounds are still scarce despite recent developments in the field. This study presents a method for skeletal editing of indoles through nitrogen atom insertion, demonstrating its utility in late-stage skeletal editing of several commercial drugs.
Article
Chemistry, Multidisciplinary
Valentina C. M. Gasser, Szabolcs Makai, Bill Morandi
Summary: This article introduces the recent applications of electrophilic aminating reagents as effective nitrogen sources for the synthesis of unprotected amino functionalities, and summarizes the strategy of introducing unprotected amino groups on different compounds. It also explains how this strategy helps to improve reaction efficiency and atom economy.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Sven Roediger, Sebastian U. Leutenegger, Bill Morandi
Summary: We present a strategy that allows for the direct substitution of tertiary phosphines. This method enables the introduction of various alkyl substituents into phosphorus-based compounds, providing a faster route for the synthesis of parent ligand derivatives.
