Article
Chemistry, Multidisciplinary
Md. Emdadul Hoque, Jin-Quan Yu
Summary: In this study, we report a new method for the gamma-arylation and gamma-lactonization of aliphatic acids, enabled by a L,X-type CarboxPyridone ligand catalyzed Pd(II) reaction. A wide range of gamma-arylated gamma-lactones can be efficiently synthesized in a single step, and the arylated lactones can be further converted into disubstituted tetrahydrofurans, which are prominent scaffolds in bioactive molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Wen-Xuan Cao, Lei Zhu, Yiyi He, Run Wang, Ming Liu, Qin Ouyang, Qing Xiao
Summary: The first aryne insertions into the carbon-iodine bond of heteroaryl iodides have been achieved. This novel reaction provides an efficient pathway for the synthesis of valuable building blocks 2-iodoheterobiaryls with excellent regioselectivity by reacting heteroaryl iodides and o-silylaryl triflates. The copper(I) catalyst, which contains a N-heterocyclic carbene (NHC) ligand, is essential for the reaction. Control reactions and DFT calculations suggest that the coordination of copper, acting as a Lewis acid, with nitrogen atoms of heteroaryl iodides mediates the aryne insertions into heteroaryl carbon-iodine bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Artem Tsymbal, Lorenzo Delarue Bizzini, David W. C. MacMillan
Summary: In this study, a dual photo/nickel catalytic manifold was described, which includes a complementary sequence involving free radical generation, radical sorting via selective binding to a Ni(II) center, and bimolecular homolytic substitution (S(H)2) at a high-valent nickel-alkyl complex. This catalytic manifold enables the elusive cross-coupling of diverse aliphatic carboxylic acids to generate valuable C(sp(3))-C(sp(3))-products. The discovery provides important insights for addressing the long-standing challenge in fragment coupling chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Thomas Sephton, Anastasios Charitou, Cristina Trujillo, Jonathan M. Large, Sam Butterworth, Michael F. Greaney
Summary: This study found that benzyne can be used to activate anilines and set up aryl transfer reactions in a single step, establishing a metal-free route to valuable biaryl products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
Yun Yang, Christopher R. Jones
Summary: Intermolecular aryne ene reactions provide opportunities for arylation of various unsaturated substrates in a single step, while intramolecular reactions offer expedient access to valuable benzo-fused carbo- and heterocyclic frameworks. This review charts the development of the aryne ene reaction, from initial reports explaining unexpected byproduct formation in competing [4+2] and [2+2] cycloadditions to its application in contemporary synthetic methodology.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Physical
Satabdi Bera, Saikat Roy, Shyam Chand Pal, Anakuthil Anoop, Rajarshi Samanta
Summary: This study demonstrates an efficient Ir(III)-catalyzed straightforward intermolecular N-arylation of acyclic aliphatic amides using quinone diazide as a coupling partner. The reaction conditions are simple and mild with a broad substrate scope, and the bidentate picolinamide group is essential for successful transformation. Mechanistic studies and DFT calculations highlight a migratory insertion-based pathway. The developed method exhibits different reactivities compared to reactions using related diazo/azide congeners under Rh(III)/Ir(III) catalysis.
Article
Chemistry, Organic
Min Liu, Haobin Jiang, Jiyuan Tang, Zenghui Ye, Fengzhi Zhang, Yanqi Wu
Summary: Here, a base-mediated, highly meta-selective O-arylation process of phenols and cyclic diaryliodonium salts without the use of transition metals is reported. This novel and practical method has been demonstrated to be useful for the synthesis of iodine-containing meta-functionalized biaryl ethers with a broad functional group tolerance and environmental friendliness. Diverse transformations of the products have been conducted to obtain various valuable functionalized biaryls. Preliminary mechanistic studies provide support for the proposed aryne generation mechanism.
Article
Chemistry, Multidisciplinary
Jadhav Rahul Dhanaji, Polasani Samatha, Silver Raju, Prathama S. Mainkar, Raju Adepu, Srivari Chandrasekhar
Summary: The aryne insertion reaction with 2-aroyl malonates/cyanoesters leads to the formation of diarylmethane or chromones, depending on the substitution on the aryne ring. Chromones are generated when an electronegative atom is present at the ortho position of arynes, while other arynes undergo a cascade double aryne insertion to form diarylmethanes.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Y. N. Sambasiva Rao, Palash Ghosh, Prathama S. Mainkar, Srivari Chandrasekhar
Summary: An efficient and metal-free strategy has been developed for the synthesis of spiro-fused indanolactones/lactams via the reaction of arynes with alpha-chloroacetyl lactones/lactams. This strategy allows for the access to spiroindanone derivatives through aryne insertion/spirocyclization.
Review
Chemistry, Multidisciplinary
Ken Kamikawa
Summary: Although arynes are usually fleeting intermediates, they are highly useful in synthetic applications due to their ability to introduce aromatic rings and form new bonds at multiple sites. Asymmetric catalysis for capturing arynes has been a challenging goal in aryne chemistry, as it requires sufficient interactions between the short-lived arynes and reactive intermediates in a stereo-controlled manner. This review highlights recent advances in asymmetric reactions using arynes, including diastereoselective, enantioselective, and catalytic enantioselective reactions.
NATURE REVIEWS CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Brylon N. Denman, Erin E. Plasek, Courtney C. Roberts
Summary: This article explores a method to achieve regioselectivity in metal-catalyzed aryne difunctionalization through catalyst control.
Article
Chemistry, Multidisciplinary
Rong Fan, Shihan Liu, Qiang Yan, Yun Wei, Jingwen Wang, Yu Lan, Jiajing Tan
Summary: Boronic acids are widely used reagents in organic synthesis, and this study demonstrates their potential as efficient substitutes for hydroxides when activated through fluoride complexation. The researchers developed a novel reaction involving aryne-induced ring-opening of cyclic sulfides and three-component coupling of fluoro-azaarenes to showcase this application. The novel hydroxy source exhibits mild activation conditions, useful functionality tolerance, and structural tunability, offering new possibilities for organoboron chemistry. Detailed computational studies shed light on the mechanistic pathway and reactivity differences of ArB(OH)(x)F-y complexes, supporting the experimental data.
Article
Chemistry, Multidisciplinary
Matteo Lanzi, Torben Rogge, Tan Sang Truong, K. N. Houk, Joanna Wencel-Delord
Summary: Hypervalent chloranes are rare and poorly explored reagents that possess unique electronic properties. This study reports highly chemo- and regioselective, metal-free, and mild C-C and C-O couplings using these chloranes. Mechanistic studies reveal the unprecedented reactivities and selectivities of these systems and the involvement of aryne intermediates. The synthetic potential of these transformations is demonstrated through post-functionalization of the coupling products obtained from chloranes and phenols under different conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Perla Ramesh, Chinnabattigalla Sreenivasulu, Dakoju Ravi Kishore, Dasari Srinivas, Koteswara Rao Gorantla, Bhabani S. Mallik, Gedu Satyanarayana
Summary: This article describes the development of a new aliphatic nitrile-template-directed remote meta-selective C-H olefin functionalization reaction of arenes. The method is feasible at room temperature and enables the formation of products with excellent regioselectivity. The efficacy and robustness of the method have been demonstrated through the synthesis of various drug analogues and gram-scale synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kotaro Yamashita, Kota Sato, Yutaka Tanji, Jun-ya Hasegawa, Tetsuaki Fujihara
Summary: Dirhodium complexes with bulky carboxylate ligands were synthesized and characterized. The steric bulk of carboxylate ligands has an impact on the selectivity in Rh-catalyzed intramolecular reactions: Rh catalysts with bulky carboxylate ligands preferentially produced five-membered ring products via insertion into a carbon-hydrogen bond, while conventional Rh catalysts obtained six-membered ring products via insertion of a carbon-carbon double bond.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
