Article
Chemistry, Multidisciplinary
Ryota Isshiki, Miki B. Kurosawa, Kei Muto, Junichiro Yamaguchi
Summary: A Ni-catalyzed aryl sulfide synthesis method was developed using 2-pyridyl sulfide as the sulfide donor, eliminating the need for odorous and toxic thiols. The Ni/dcypt catalyst played a crucial role in the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, with mechanistic studies showing its ability to undergo oxidative additions and ligand exchanges simultaneously.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Mengna Zhao, Qian Miao
Summary: The B3N6-[4]triangulene, a key structural unit of BC4N, was successfully synthesized through nitrogen-directed borylation, showing hydrogen-bonding properties. Its slightly bent triangular polycyclic framework consists of 4 pi-electron N-B-N units and forms hydrogen bonds with other molecules like halide or carboxylate anions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Matthew L. Martin, Claire Wilson, Alistair Boyer
Summary: Unsaturated N-2-sulfonyl amidines are converted into valuable N-heterocyclic products through heating with BF2OTf. Mechanistic studies suggest a domino 1,7-H shift that activates a C-H bond, followed by electrocylisation, resulting in stereodefined cyclic amidines.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Shanping Chen, Kai Hu, Wei Feng, Guojiang Mao, Yuxia Li, Guo-Jun Deng
Summary: A direct strategy for the synthesis of fused thienoindoles from substituted indoles and elemental sulfur has been reported. This method yields a range of structurally valuable fused thienoindoles in 51-78% yield under transition-metal-free conditions, potentially useful in pharmaceutical industry and organic functional materials.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Elisabetta Rosadoni, Elena Bombonato, Antonio Del Vecchio, Sara Guariento, Paolo Ronchi, Fabio Bellina
Summary: This note discusses the application of a Minisci-type reaction for the direct alkylation of azoles with carboxylic acids as radical precursors. Different reaction conditions were investigated to achieve high yield of the desired products, focusing on acid strength and solvent screening. Moreover, the reactivity of imidazoles with various carboxylic acids was investigated, showing good yield for most cases. The study reveals the potential of this approach for late-stage functionalization in drug discovery.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Licheng Wu, Jingping Qu, Yifeng Chen
Summary: Here, a Pd-catalyzed isomerization of alicyclic allyl amine to achieve alpha, beta-difunctionalization of synthetically inaccessible trisubstituted cyclic enamine is reported. The in situ formed enamine intermediate plays a dual role, enabling intermolecular formal [4 + 2] reaction with acrylamide or isatoic anhydride to simultaneously construct C-C and C-N bonds, leading to the expedient construction of [4.3.0]-aminal with excellent diastereoselectivity and high atom economy.
Article
Chemistry, Organic
PothapragadaS. K. Prabhakar Ganesh, Perumal Muthuraja, Purushothaman Gopinath
Summary: We report a Rh(III)-catalyzed redox-neutral C-H activation/[5+2] annulation of aroyl hydrazides with sulfoxonium ylides as safe carbene precursors. The reaction exhibits excellent functional group tolerance, broad substrate scope, and scalability. We demonstrate the synthetic utility of this protocol through the synthesis of various diazepam drug analogues, late-stage functionalization of probenecid drug, and large-scale synthesis. Kinetic studies reveal C-H activation as the rate-determining step.
Article
Chemistry, Multidisciplinary
Yuk-Cheung Chan, Marcus H. Sak, Scott A. Frank, Scott J. Miller
Summary: In this study, an organocatalytic enantioselective functionalization of heterocyclic carboxaldehydes via the Pictet-Spengler reaction was reported. A range of heterocycles could be tolerated by careful pairing of novel squaramide and Bronsted acid catalysts, leading to the synthesis of a series of heterocycle conjugated beta-(tetrahydro)carbolines with good yield and enantioselectivity. The utility of this method was demonstrated through the stereoselective preparation of pyridine-containing analogues of potent selective estrogen receptor downregulator and the U.S. FDA approved drug Tadalafil in three steps.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xin-Lian Liu, You-Ya Zhang, Lin Li, Lu-Qi Tan, Yin-Ai Huang, Ai-Jun Ma, Jin-Bao Peng
Summary: In this study, a palladium-catalyzed ligand-controlled selective addition and cycloaddition reaction was developed for the preparation of organic compounds.
Article
Chemistry, Organic
Kana Sakamoto, Takahiro Nishimura
Summary: This study describes a highly enantioselective intramolecular hydroarylation reaction using C-H activation, catalyzed by an iridium catalyst and a chiral bisphosphine ligand. The carbonyl group of ketones serves as an effective directing group, allowing for efficient synthesis of chiral 3-substituted dihydrobenzofurans in high yields and enantioselectivity from readily available starting materials. The reaction showcases the potential for developing a more efficient and selective variant of the reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Luis G. Ardon-Munoz, Jeanne L. Bolliger
Summary: This review presents a new method for the synthesis of N-arylated and N-alkylated benzo[4,5]thiazolo[2,3-c][1,2,4]triazol-1-ium salts from stable precursors, along with an expanded substrate scope. The N-aryl substituted precursors are obtained through a catalytic N-arylation reaction, while N-alkyl substituted precursors are prepared via a nucleophilic substitution reaction. The selective deprotection of the para-methoxybenzyl protected precursor leads to the formation of fused aromatic heterocycles through oxidative C-H functionalization of the linked 1,2,4-triazolium salt. The reaction tolerates a wide range of functional groups.
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS
(2023)
Article
Chemistry, Organic
Leilei Cao, Liliang Huang, Xianjun Xu, Erik V. Van der Eycken, Huangdi Feng
Summary: A novel method for the construction of nitrogen-tethered 1,6-enynes with high atom economy and exclusive chemoselectivity has been developed. Experimental studies suggest that the key step in this methodology is the alkyne-iminium ene reaction involving an intermolecular hydride transfer.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Meghan J. Oddy, Daniel A. Kusza, Ryan G. Epton, Jason M. Lynam, William P. Unsworth, Wade F. Petersen
Summary: This study reports the synthesis of 2-azetidinones (beta-lactams) from simple acrylamide starting materials through visible-light-mediated energy transfer catalysis. The reaction involves a C(sp(3))-H functionalization via a variation of the Norrish-Yang photocyclization, which includes a carbon-to-carbon 1,5-hydrogen atom transfer. Deuterium labelling and DFT calculations support this mechanism, and the reaction can be used to construct a diverse range of beta-lactam products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
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, Multidisciplinary
Mateusz Dyguda, Artur Przydacz, Lukasz Albrecht
Summary: This manuscript describes the application of dearomative formal normal-electron-demand aza-Diels-Alder cycloaddition in the synthesis of tetrahydrofuropyridines. The developed approach utilizes aminocatalytic activation of 2-alkyl-3-furfurals that proceeds via formation of the dearomatized dienamine intermediate. The obtained cycloadducts can be further transformed into tetrahydrofuropyridines or functionalized cinnamates.
CHEMICAL COMMUNICATIONS
(2023)
