Article
Chemistry, Multidisciplinary
Jun Tang, Jingxi He, Sheng-Yin Zhao, Weiping Liu
Summary: Here, we report a manganese-catalyzed three-component coupling reaction for the synthesis of beta,beta-methylated/alkylated secondary alcohols. Our method efficiently constructs assembled alcohols with high chemoselectivity in moderate to good yields using a series of 1-arylethanol, benzyl alcohol derivatives, and methanol. Mechanistic studies suggest that the reaction proceeds via methylation of a benzylated secondary alcohol intermediate to generate the final product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Feixiang Sun, Jiamin Huang, Zhihong Wei, Conghui Tang, Weiping Liu
Summary: A homogeneous manganese-catalyzed cross-coupling reaction of secondary alcohols was developed for the synthesis of gamma-disubstituted alcohols and beta-disubstituted ketones. The protocol, using Mn-MACHO(Ph) as the catalyst, exhibited a wide substrate scope and good functional group tolerance, resulting in diverse valuable disubstituted alcohols and ketones in moderate to good yields. The selective formation of alcohol products was found to be influenced by reaction temperature, with alcohols favored over ketones at lower temperatures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
C. M. A. Afsina, Thaipparambil Aneeja, Mohan Neetha, Gopinathan Anilkumar
Summary: Copper-catalyzed organic reactions have attracted widespread attention due to the abundance and affordability of copper, as well as its low toxicity, eco-friendliness, sustainable nature, and versatility as a catalyst. These reactions are primarily used for the synthesis of biologically important nitrogen heterocycles, amines, amides, imines, and alkynes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ruixin Liu, Xiaojuan Liu, Tanyu Cheng, Yaofeng Chen
Summary: Alkynylsilanes are important organic compounds that can be synthesized through dehydrogenative coupling of hydrosilanes with terminal alkynes, and the use of organocalcium complexes in organic synthesis has been gaining increasing attention.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Siba P. Midya, Murugan Subaramanian, Reshma Babu, Vinita Yadav, Ekambaram Balaraman
Summary: This study reports a nickel-catalyzed acceptorless dehydrogenative coupling reaction, which can access diverse substituted olefins. The method features a low-cost catalyst, good functional group compatibility, and high reaction selectivity and efficiency.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Amreen K. Bains, Ayanangshu Biswas, Debashis Adhikari
Summary: The study describes an isolable, air-stable homogeneous nickel catalyst for dehydrogenative cross-coupling reaction between secondary and primary alcohols to selectively produce alpha-alkylated ketone products in a one-pot reaction. Preliminary mechanistic investigation suggests a radical mechanism following borrowing hydrogen reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Multidisciplinary
Alexis Tabey, Pooja Y. Vemuri, Frederic W. Patureau
Summary: The high electronegativity of nitrogen presents challenges for N-N bond forming cross-coupling reactions, especially in an intermolecular fashion. Dehydrogenative N-N coupling reactions are advantageous in terms of step and atom economy, but require careful design of an oxidizing system to avoid unwanted side reactions. Despite the importance of N-N bonds in organic chemistry, only a few intermolecular hetero N-N cross-dehydrogenative couplings exist, highlighting the need for further research in this area.
Article
Chemistry, Physical
Aniekan Ekpenyong Owen, Annika Preiss, Angus McLuskie, Chang Gao, Gavin Peters, Michael Buehl, Amit Kumar
Summary: Urea derivatives and polyureas are important compounds with diverse applications. However, the conventional synthesis methods involving toxic reagents pose risks to the environment and human health. In this study, a catalytic reaction using safer reagents was developed to synthesize urea derivatives and polyureas. The method demonstrated high efficiency and atom economy, achieving moderate to quantitative yields of various compounds. Mechanistic insights were also provided through experiments and computational analysis.
Article
Chemistry, Multidisciplinary
Tao Zhong, Chengyihan Gu, Yuhang Li, Jun Huang, Jian Han, Chengjian Zhu, Jie Han, Jin Xie
Summary: In this paper, a novel bimetallic relay catalysis of Mn2(CO)10 and cobaloxime has been developed for the divergent dehydrogenative difluoroalkylation of alkenes using commercially available difluoroalkyl bromides. A wide range of structurally diverse difluoroalkylated allylic products and difluoromethylated cyclic products were efficiently synthesized, accompanied with the production of H2 as the by-product. This bimetallic relay strategy features broad substrate scope, mild reaction conditions, and excellent functional group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Satyadeep Waiba, Kakoli Maji, Mamata Maiti, Biplab Maji
Summary: In this study, we present a simple synthesis method for valuable alpha-hydroxycarboxylic acid molecules through an acceptorless dehydrogenative coupling of ethylene glycol and primary alcohols. A stable manganese complex catalyst facilitated the reaction, which showed scalability and high yields with excellent selectivities under mild conditions. The protocol is environmentally friendly, generating only water and hydrogen gas as byproducts. Furthermore, it was successfully applied to synthesize various drugs and bioactive molecules, demonstrating its broad applicability and potential in organic synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Anne Renault, Lionel Joucla, Emmanuel Lacote
Summary: In this study, a catalytic formation of 2-tetrazenes was reported, which involved the copper (ii) promoted oxidation of hydrazines in the presence of bipyridine ligands using air or dioxygen as the terminal oxidant. The method successfully produced symmetrical tetrazenes, which were previously prepared using toxic or stoichiometric oxidants. Additionally, the catalytic reaction could be used for the formation of cyclic tetrazenes and dissymmetric structures under certain conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Tao Li, Hong Zhang, Albert S. C. Chan, Shan-Shui Meng
Summary: In this study, a dimanganese decacarbonyl-catalyzed dehydrogenative coupling of silanes and hydroxyl compounds has been developed using inexpensive phosphine oxide ligands. The reaction exhibits a broad substrate scope and yields the corresponding silyl ethers and silanols in moderate to high yields (>91 examples, up to 99% yield). Additionally, N-silylated indoles are successfully synthesized through direct dehydrogenative coupling of N-H bonds and silanes. Mechanistic studies reveal an unusual organometallic pathway controlled by the phosphine oxide ligand.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Review
Chemistry, Inorganic & Nuclear
Ishani Borthakur, Anirban Sau, Sabuj Kundu
Summary: Functionalization of alcohols is a promising field in synthesis due to their easy availability from biomass, with cobalt emerging as a promising candidate for its exceptional catalytic activity, unique redox behavior, and diverse reaction mechanism.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Organic
Ke Yu, Qianjin Chen, Weiping Liu
Summary: An atom-economical and straightforward methodology for the synthesis of quinolines from alpha-2-aminoaryl alcohols and secondary alcohols is described. This protocol uses an Earth-abundant and air-stable iron catalyst under activating agent-free conditions, resulting in high yields and good functional group tolerance. Notably, the method allows for the synthesis of highly substituted fused polycyclic quinolines using secondary alpha-2-aminoaryl alcohols and beta-substituted secondary alcohols, achieving up to 94% isolated yields.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Pei Fan, Yujia Mao, Chuan Wang
Summary: Herein, we report a palladium/TBADT-cocatalyzed dehydrogenative cross-coupling reaction that enables the synthesis of various 1,4-diketones from simple allylic alcohols and aldehydes as precursors under mild reaction conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Amit Kumar, Trevor Janes, Subrata Chakraborty, Prosenjit Daw, Niklas von Wolff, Raanan Carmieli, Yael Diskin-Posner, David Milstein
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Multidisciplinary
Jesus A. Luque-Urrutia, Miguel Sola, David Milstein, Albert Poater
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Physical
Uttam Kumar Das, Yehoshoa Ben-David, Gregory Leitus, Yael Diskin-Posner, David Milstein
Article
Chemistry, Physical
Judit Masdemont, Jesus A. Luque-Urrutia, Marti Gimferrer, David Milstein, Albert Poater
Article
Chemistry, Multidisciplinary
Yinjun Xie, Peng Hu, Yehoshoa Ben-David, David Milstein
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Multidisciplinary
Shan Tang, Niklas von Wolff, Yael Diskin-Posner, Gregory Leitus, Yehoshoa Ben-David, David Milstein
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Uttam Kumar Das, Amit Kumar, Yehoshoa Ben-David, Mark A. Iron, David Milstein
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Prosenjit Daw, Amit Kumar, Noel Angel Espinosa-Jalapa, Yehoshoa Ben-David, David Milstein
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Physical
You-Quan Zou, Niklas von Wolff, Aviel Anaby, Yinjun Xie, David Milstein
Article
Chemistry, Applied
Uttam Kumar Das, Sayan Kar, Yehoshoa Ben-David, Yael Diskin-Posner, David Milstein
Summary: The first example of homogeneously catalyzed hydrogenation of the N=N bond of azo compounds has been reported using a complex of an earth-abundant-metal. The hydrogenation reaction is catalyzed by a manganese pincer complex, proceeds under mild conditions, and yields amines, which makes this methodology a sustainable alternative route for the conversion of azo compounds. A plausible mechanism involving metal-ligand cooperation and hydrazine intermediacy is proposed based on mechanistic studies.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Yaoyu Liang, Uttam Kumar Das, Jie Luo, Yael Diskin-Posner, Liat Avram, David Milstein
Summary: This article presents a catalyst based on magnesium complexes and explores its potential in environmentally friendly organic transformations through metal-ligand cooperation for hydrogen activation. The catalyst showed remarkable performance in semihydrogenation of alkynes and hydrogenation of alkenes, providing high yields and selectivities.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ramaraj Ayyappan, Uttam Kumar Das, Issam Abdalghani, Rosenildo C. Da Costa, Graham J. Tizzard, Simon J. Coles, Gareth R. Owen
Summary: The reaction between 6-DiPPon and [RuCl2(p-cymene)]2 resulted in the formation of two complexes with different ligands, the ratio of which can be controlled by the solvent used. In the presence of AgOTf and Na[BArF24], two other complexes were formed. The properties and reaction mechanisms of these new ligands and complexes have important implications for catalyst activity and applications.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Uttam Kumar Das, Trevor Janes, Amit Kumar, David Milstein
Article
Chemistry, Physical
Yinjun Xie, David Milstein
ACS APPLIED ENERGY MATERIALS
(2019)