Article
Chemistry, Multidisciplinary
Miran Lemmerer, Haoqi Zhang, Anthony J. Fernandes, Tobias Fischer, Marianne Miesskes, Yi Xiao, Nuno Maulide
Summary: Herein, we present a method for the synthesis of alpha-aryl acrylamides through polar S-to-C aryl migrations induced by a Lewis basic organocatalyst. This polar process allows subsequent elimination reactions, leading to a formal aryl/hydrogen exchange, including SO2 extrusion. The reaction is selective for electron-deficient aromatic groups and can tolerate a variety of substituents on nitrogen and in the beta-position, providing useful building blocks for further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Renzo Rossi, Maurizio Ciofalo
Summary: This review gives a comprehensive overview of the Pd-catalysed intermolecular direct C-H bond arylation of heteroarenes with arylating reagents. It summarizes the preparation of various arylating reagents, evaluates the practicality, versatility, and limitations of the arylation protocols, and compares the results with reactions using aryl halides as electrophiles. Mechanistic proposals are also discussed.
CURRENT ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Da-Liang Zhu, Jie Li, David James Young, Yanqing Wang, Hong-Xi Li
Summary: This paper presents a mild strategy for aminating aryl halides with anilines using dual photoredox and nickel catalysis. Thioxanthen-9-one, an inexpensive and readily available compound, greatly enhanced this cross-coupling reaction, yielding a diverse range of diarylamines in good yields (41-93%) at room temperature. The reaction could be performed under compact fluorescent lamp light or sunlight and was tolerant of various functional groups. It was successfully applied to the synthesis of natural products and drug molecules, even at a gram-scale. The mechanism involves several steps including oxidative addition, transmetalation, energy transfer, and reductive elimination.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Alexis L. Gabbey, Nicholas W. M. Michel, Jonathan M. E. Hughes, Louis-Charles Campeau, Sophie A. L. Rousseaux
Summary: In this study, a new strategy was reported for the synthesis of secondary α-aryl amides through a nickel-catalyzed reductive arylation reaction using N-hydroxyphthalimide (NHP) esters of malonic acid half amides as redox-active substrates. This method proceeds under mild conditions and exhibits excellent chemoselectivity for amide α-arylation in the presence of other enolizable carbonyls.
Article
Chemistry, Organic
Baptiste Picard, Takahide Fukuyama, Ilhyong Ryu
Summary: An improved carbonylation method for amide bond formation between aryl iodides and aromatic amines is presented, which does not require a phosphine ligand unlike conventional Pd catalysis. The catalyst system consists of bis(dibenzylideneacetone)palladium (0.5 mol %) and DBU (10 mol %). This method allows the synthesis of various aromatic amides and can be scaled to gram order synthesis under low carbon monoxide pressure.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kartic Manna, Ranjan Jana
Summary: We describe a mild and highly selective palladium-catalyzed cross-electrophile coupling between aromatic diazonium salts and aryl iodides or diaryliodonium salts in a water-ethanol (2:1) medium. Mechanistic studies revealed the importance of ethanol in generating an active Pd(0) catalyst, and the counterion of the diazonium salt promotes the formation of a cationic Pd(II) species that facilitates subsequent oxidative addition to aryl iodides/diaryliodonium salts. The presence of silver(I) salt is crucial for maintaining the catalytic activity of palladium by removing iodide ions as precipitates.
Article
Chemistry, Organic
Hua Yao, Xiaoyang Zhong, Bingqing Wang, Sen Lin, Zhaohua Yan
Summary: A novel and efficient approach for the amine-directed dehydrogenative C(sp(2))-C(sp(3)) coupling of arylamines with acetonitrile was developed using FeCl2 as the catalyst. The method provides a straightforward and green route to arylacetonitriles with good regioselectivity and excellent compatibility of functional groups and aromatic rings.
Article
Chemistry, Physical
Florian Papp, Daniel Sowa Prendes, Sourav Manna, Ann-Katrin Seitz, Sofiya Kostiukovska, Julian Loeffler, Viktoria H. Gessner, Lukas J. Goossen
Summary: Palladium complexes with ylide-functionalized phosphine ligands catalyze the arylation of N-protected hydantoins with aryl chlorides, enabling the synthesis of a wide variety of hydantoins, including derivatives of the anticonvulsant drugs phenytoin and mephenytoin. Selective monoarylations, sequential diarylations, and arylation-alkylation sequences have been achieved, along with stepwise deprotection strategies.
Article
Chemistry, Organic
Torben Rogge, Thomas Mueller, Hendrik Simon, Xiaoyan Hou, Simon Wagschal, Diego Broggini, Lutz Ackermann
Summary: A triazole-directed direct C-H arylation of arenes with electron-deficient aryl halides or pyrimidyl chloride was achieved through ruthenium catalysis. This strategy provides a simple and environmentally friendly access to highly functionalized hetarenes, avoiding the use of strong organometallic bases. Detailed studies revealed a significant impact of the phosphine ligand, enabling the reaction to exhibit excellent levels of chemo- and position selectivity.
Article
Chemistry, Multidisciplinary
Daniel Sowa Prendes, Florian Papp, Nagesh Sankaran, Nardana Sivendran, Frederike Beyer, Christian Merten, Lukas J. Goossen
Summary: Arylglycines, which are important pharmacophores in several top-selling drugs, can now be synthesized from abundant aryl chlorides using a Pd-catalyzed Schollkopf-type amino acid synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Fusheng Bie, Xuejing Liu, Han Cao, Yijun Shi, Tongliang Zhou, Michal Szostak, Chengwei Liu
Summary: The Pd-catalyzed double-decarbonylative synthesis of aryl thioethers involves an aryl exchange reaction between amides and thioesters, with amides serving as aryl donors and thioesters as sulfide donors. The use of Pd/Xantphos without any additives promotes aryl exchange by C(O)-N/C(O)-S cleavages, allowing for a wide variety of amides and sulfides to be used in the reaction.
Article
Chemistry, Organic
Jian Zhang, Xinzhe Shi, Henri Doucet
Summary: This study explores a Pd-catalyzed annulative pi-extension reaction of 1-arylpyrroles using 1,2-dihalobenzenes as coupling partners, leading to the selective synthesis of pyrrolo[1,2-f]phenanthridines. The higher reactivity of the pyrrole C2-H bond allows for successful access to substituted pyrrolo[1,2-f]phenanthridines.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Xianglin Luo, Zhewei Li, Yuzhen Zheng, Yueping Lin, Huanfeng Jiang, Lukas J. Goossen, Ming Lei, Liangbin Huang
Summary: Directed C-H arylations are widely used strategies for the synthesis of biaryls. However, their sensitivity to steric hindrance is a limitation. In this study, a ruthenium catalyst is used to overcome this limitation and achieve high yields of ortho-C-H arylation. The combination of a carboxylate directing group and chelating N-ligand is found to be crucial for the selectivity of the reaction.
Article
Chemistry, Multidisciplinary
Hai-Yun Huang, Amal Benzai, Xinzhe Shi, Henri Doucet
Summary: Researchers are focused on developing different procedures for direct functionalization of two different C-H bonds of the same organic molecule, which is currently an important research topic in organic chemistry. Over the past decade, the number of tools to control regiodivergent C-H bond functionalizations has significantly increased.
Article
Chemistry, Applied
Bingxiang Xue, Jie Shen, Sourav Manna, Angelino Doppiu, Lukas J. Goossen
Summary: A new catalyst has been discovered that can selectively introduce a primary amino group into aromatic compounds, and it can efficiently promote the amination reaction to synthesize primary anilines within 30 minutes.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
