Article
Chemistry, Organic
Xin Du, Huan Zhao, Xinling Li, Lizhi Zhang, Yunhui Dong, Ping Wang, Daopeng Zhang, Qing Liu, Hui Liu
Summary: The ligand-regulated regiodivergent hydroarylation of the distal double bond of allenamides with aryl boronic acid was achieved in the presence of palladium(II) catalysts, leading to the formation of various functionalized enamide with excellent E selectivity and Markovnikov/antiMarkovnikov selectivity.Coordination intermediates play a crucial role in determining the selectivity of the reaction, with different intermediates leading to different regioselectivities and product distributions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Pedro P. De Castro, Gabriel M. F. Batista, Giovanni W. Amarante, Helio F. Dos Santos
Summary: Theoretical calculations and control experiments were used to investigate the mechanism and origin of enantioselectivity in the phosphoric-acid-catalyzed dynamic kinetic resolution of azlactones. The results identified a Munchnone intermediate as crucial in the isomerization of azlactone rings, and the developed model successfully predicted enantioselectivity under various reaction conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Robert J. Harris, Kohki Nakafuku, Alethea N. Duncan, Robert G. Carden, Jacob C. Timmerman, Ross A. Widenhoefer
Summary: The mechanism of intermolecular hydroamination of 3-methylbuta-1,2-diene with N-methylaniline catalyzed by (IPr)AuOTf has been studied, revealing a complex process involving reversible displacement reactions and the formation of cationic gold complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Maurizio Chiminelli, Andrea Serafino, Davide Ruggeri, Luciano Marchio, Franca Bigi, Raimondo Maggi, Max Malacria, Giovanni Maestri
Summary: Dearomative cycloadditions offer a powerful method to access a vast chemical space using simple and ubiquitous building blocks. However, the loss of aromaticity has limited their synthetic potential. We have devised a general intramolecular method that overcomes this limitation by photosensitizing allenamides. This visible-light-promoted process produces complex [2.2.2]-(hetero)-bicyclooctadienes at room temperature, potentially stabilizing transient (bi)radicals through naphthalene. The reaction is tolerant of various functional groups, making it suitable for a wide range of applications, including the synthesis of isoindoles and metal complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Dino Berthold, Bernhard Breit
Summary: A concise synthesis of (R)-sitagliptin monophosphate, a drug used for treating type 2 diabetes, was reported. A new approach for the construction of the inherent chiral amino function was established on a 3.5 mmol scale using the Rh-I-catalyzed hydroamination of allenes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Srinivasarao Yaragorla, Dandugula Sneha Latha, Pallava Rajesh
Summary: The study introduced a simple and efficient One-Pot three-component reaction using tert-propargyl alcohols, primary amines, and acyl ketones to synthesize fully substituted pyrroles and pyridine derivatives. A green calcium catalyst was employed to facilitate the formation of β-amino allene intermediate, leading to fully substituted five and six-membered azacyclic compounds through subsequent hydroamination and deacylation reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Teng Jia, Shengyu Fan, Fengmian Li, Xiaohan Ye, Wenke Zhang, Zhiguang Song, Xiaodong Shi
Summary: The intermolecular hydro-amination of arylalkynes with aliphatic amine catalyzed by a combination of 1,2,3-triazole-coordinated gold(I) catalyst and Zn(OTf)(2) cocatalyst has been successfully achieved with good to excellent yields and regioselectivity. Compared to previous methods, this approach offers an alternative catalyst system for this fundamental chemical transformation with high efficiency and practical conditions.
Article
Chemistry, Multidisciplinary
Qiuyu Li, Xinxin Fang, Rui Pan, Hequan Yao, Aijun Lin
Summary: This study reports a Pd-catalyzed sequential hydroamination reaction that can efficiently synthesize various imidazolidinones, thiadiazolidines, and imidazolidines. Asymmetric sequential hydroamination generates a series of enantioenriched imidazolidinones with synthetic value.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yong Wu, Shanshan Cao, Iskander Douair, Laurent Maron, Xihe Bi
Summary: The [2+1] cycloaddition reaction of a metal carbene with an alkene often suffers from side reactions, leading to lower yields of cyclopropanation products. By adding a low concentration of diazo compound to alkenes, it was found that AgOTf catalysis can efficiently produce cyclopropane products from hindered alkenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Marin Puget, Viacheslav Shcherbakov, Sergey Denisov, Philippe Moreau, Jean-Pierre Dognon, Mehran Mostafavi, Sophie Le Caer
Summary: The nature of the primary species formed in FEC depends on the amount of FEC in the solution, which will affect its performance in the electrolyte.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Zhiyao Duan, Graeme Henkelman
Summary: This study uses global optimization and constant-potential density functional theory to simulate the complete process of Pt dissolution, revealing the formation and dissolution mechanism of a two-dimensional Pt surface oxide. The findings provide a fundamental understanding of Pt dissolution under potential cycling, which is essential for the rational design of durable Pt-based cathodes for fuel cells.
Article
Chemistry, Multidisciplinary
Raphael Robidas, Claude Y. Legault
Summary: A mechanism is proposed to explain the formation of benzobicyclo[3.2.0]heptane derivatives from 1,7-enyne derivatives bearing a terminal cyclopropane, which has been previously reported.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Engineering, Environmental
Nannan Wu, Mingzhu Liu, Bingru Tian, Zunyao Wang, Virender K. Sharma, Ruijuan Qu
Summary: In this study, the oxidation of five phenolic contaminants using ferrate(VI) was investigated to understand the reaction mechanisms. Experimental and theoretical calculations revealed that the reaction rate constants were correlated with the energy of the highest occupied molecular orbital. Electron-donating groups (-R) were found to be more easily oxidized by ferrate(VI) compared to weak electron withdrawing groups (-X) and strong electron-withdrawing groups (-(C=O)-). The dominance of Fe(VI) in the reaction process was determined, and four main reaction mechanisms, including single-oxygen transfer, double-oxygen transfer, ·OH attack, and electron-transfer-mediated coupling reaction, were proposed. Density functional theory calculations suggested that the presence of -(C=O)- facilitated the occurrence of double-oxygen transfer and ·OH attack reactions, while the tendency of single-oxygen transfer and electron-transfer reaction varied with different substituents. Furthermore, the double-oxygen transfer pathway was found to be a common reaction mechanism during the ferrate(VI) oxidation of phenolic compounds.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Organic
Ke-Qin Wu, Hui Li, Ao Zhou, Wei-Ran Yang, Qin Yin
Summary: A Pd-catalyzed regioselective C-H bond allylic alkylation of phenols with 1,3-dienes is reported, which selectively functionalizes the ortho C-H bond of 2-naphthols, 1-naphthols, and electron-rich phenols to synthesize phenol derivatives with diverse structures. The reaction is accelerated by a diphosphine ligand, does not require any other additive, and exhibits broad substrate scope and good chemo- and regioselectivity. Additionally, an asymmetric variant is investigated, achieving product with up to 55% enantiomeric excess.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
B. B. Xiao, L. Yang, H. Y. Liu, X. B. Jiang, B. Aleksandr, E. H. Song, Q. Jiang
Summary: The study systematically investigates the oxygen reduction reaction and oxygen evolution reaction of graphene materials embedded with TMN4 clusters (TM = Fe, Co, Ni) using density functional theory calculations. It demonstrates that the functionalization of graphene can dramatically alter the activity and stability of TMN4 clusters, offering new insights into the design of bifunctional oxygen electrodes.
APPLIED SURFACE SCIENCE
(2021)