Article
Chemistry, Organic
Peng-Cheng Cui, Zheng-Chun Yin, Guan-Wu Wang
Summary: The visible-light-promoted C4-selective phosphorylation of unprefunctionalized pyridine and quinoline derivatives has been achieved. This Minisci-type protocol offers highly regioselective access to C4-phosphorylation products with good functional group tolerance and moderate to good yields via cross dehydrogenation coupling under mild conditions. Mechanistic studies demonstrate that the C4-phosphorylation products are obtained through a radical pathway.
Article
Chemistry, Inorganic & Nuclear
Lingying Meng, Yujiao Dong, Bo Zhu, Yujie Liang, Zhongmin Su, Wei Guan
Summary: This study reveals a unique radical mechanism activated by decatungstate as a photocatalyst, which can successfully construct C(sp(3))-C(sp(2)) bonds. This mechanism involves hydrogen atom transfer and proton-coupled electron transfer reactions.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Ahmet Yesilcimen, Na-Chuan Jiang, Felix H. Gottlieb, Masayuki Wasa
Summary: Here, we present a catalytic method for the selective coupling of alkyl ethers and heterodienes, enabling the rapid synthesis of dihydropyran derivatives with multiple stereocenters.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Yi-Xin Xu, Yu-Qing Liang, Zhong-Jian Cai, Shun-Jun Ji
Summary: A novel chelation-assisted C-H arylation reaction of benzo[h]quinoline is described in this study. The reaction, using [RuCl2(p-cymene)]2 as the catalyst and cheap and easily accessible arylsulfonyl chlorides as the arylation source, exhibits simple reaction conditions, a broad substrate scope, and good functional group tolerance. The successful application of bioactive-molecule-based sulfonyl chlorides further emphasizes the potential utility and importance of this desulfitative C-H arylation protocol.
Article
Chemistry, Organic
Austin D. Marchese, Andrew G. Durant, Mark Lautens
Summary: A simple and modular approach using palladium catalysis to synthesize bis-heterocyclic spirocycles is reported. The method leverages a Mizoroki-Heck-type reaction to generate neopentylpalladium species, allowing for intramolecular C-H activation on a wide array of C-H bonds to produce a variety of spirocycles. The reaction is scalable, allowing for easy incorporation of biologically relevant heterocycles without the need for flash column chromatography.
Article
Chemistry, Physical
Amal Benzai, Fazia Derridj, Henri Doucet, Jean-Francois Soule
Summary: The study reports a Pd- or Ru-catalyzed arylation reaction that allows for the ortho-arylation of the aryl unit of 2-arylpyrazines with high regioselectivity and applicability to various substituted pyrazine compounds. Experimental results demonstrate that even pyrazines with 2,3-diphenyl substitution can yield the desired arylated product.
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, 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, Organic
Smruti Ranjan Mohanty, Namrata Prusty, Tanmayee Nanda, Shyam Kumar Banjare, Ponneri C. Ravikumar
Summary: In this study, the ruthenium-catalyzed regioselective sp2(C-H) monoalkenylation of N-arylpyridones was demonstrated, where the pyridone served as a weakly coordinating directing group. Importantly, this methodology was effectively applied to the synthesis of various drug analogues, with high yields up to 93%. HRMS analysis also revealed the presence of a six-membered ruthenium complex.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Jayabrata Das, Wajid Ali, Debabrata Maiti
Summary: In this review, the development of C(sp3)-H activation is highlighted, including its origins, progression, and overcoming of limitations, to identify future research directions. The three main strategies for C(sp3)-H activation in aliphatic molecules are static directing group (DG) or template-assisted approach, transient DG (TDG) approach, and native functional group (NFG)-assisted approach. Each section provides a brief discussion on the evolution, functionalization type, advantages, and shortcomings of C(sp3)-H activation.
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Applied
Paula Andrade-Sampedro, Jon M. Matxain, Arkaitz Correa
Summary: The development of catalytic tools for the late-stage modification of amino acids within a peptide framework is challenging but important. The researchers reported a Ru-catalyzed C(sp(2))-H hydroxylation method for di- and tripeptides containing tyrosine, using a carbamate as a removable directing group and PhI(OCOCF3)(2) (PIFA) as an oxidant. This method is reliable, scalable, and enables the synthesis of L-DOPA peptidomimetics without racemization. Density Functional Theory calculations support the proposed catalytic cycle involving Ru(II)/Ru(IV).
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Sumit Garai, Devarajulu Sureshkumar
Summary: In this study, a palladium-catalyzed efficient and versatile method for C(sp(2))-H ortho-cyanomethylation of arylamides with a broad substrate scope and moderate to excellent yields was developed. An inexpensive and commercially available chloroacetonitrile was used as the cyanomethylating source. The synthetic feasibility of this technique was also demonstrated by gram-scale synthesis and functional group transformation of the products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sumit Garai, Devarajulu Sureshkumar
Summary: In this study, a palladium-catalyzed and versatile method for ortho-cyanomethylation of arylamides with a broad substrate scope and moderate to excellent yields was developed. Chloroacetonitrile, which is inexpensive and commercially available, was used as the cyanomethylating source. The method is also compatible with the air atmosphere. Furthermore, the synthetic feasibility of this technique was demonstrated through gram-scale synthesis and functional group transformation of the products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Gopal Krushna Das Adhikari, Smruti Ranjan Mohanty, Shyam Kumar Banjare, Namrata Prusty, Gajiram Murmu, Ponneri C. Ravikumar
Summary: In this study, a method for synthesizing beta-carboline-1-one derivatives from indole-2-carboxamides and bicycloalkenes under mild conditions is reported. The commercially available ruthenium catalyst was used for the reaction. The reaction showed good tolerance towards various functional groups and resulted in high yields of the desired products. Mechanistic studies revealed the involvement of a reversible cyclometalation pathway.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Medicinal
Zhou Xu, Yang Xie, Pei Hu, Xiao-Ting Tian, Yi-Hong Lu, Hao-Dong Jiang, Cheng-Gang Huang, Zhi-Cai Shang
Summary: We outline a concise and efficient method for synthesizing the isodityrosine unit of seongsanamide A-D and its derivatives, utilizing palladium-catalyzed C(sp(3))-H functionalization and a Cu/ligand-catalyzed coupling reaction. This study introduces a practical protocol for the palladium-catalyzed mono-arylation of β-methyl C(sp(3))-H of an alanine derivative, which allows for the synthesis of various β-aryl-α-amino acids. These acids can then be converted into diverse tyrosine and DOPA derivatives. Furthermore, a CuI/N,N-dimethylglycine-catalyzed arylation with aryl iodides is described for the synthesis of isodityrosine derivatives.
