Article
Chemistry, Multidisciplinary
Xia Hu, Ivan Cheng-Sanchez, Sergio Cuesta-Galisteo, Cristina Nevado
Summary: An electrochemically driven nickel-catalyzed enantioselective reductive cross-coupling reaction was developed for the synthesis of enantioenriched beta-aryl homoallylic amines with excellent E-selectivity. This reaction proceeds under mild conditions without the use of heterogeneous metal reductants and sacrificial anodes, employing constant current electrolysis with triethylamine as a terminal reductant. The reaction demonstrates remarkable stereocontrol, broad substrate scope, and excellent functional group compatibility, making it suitable for the late-stage modification of bioactive molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Juan Feng, Jiayi Shi, Lan Wei, Mingqing Liu, Zhiming Li, Yuanjing Xiao, Junliang Zhang
Summary: In this study, a highly regio- and diastereo-selective palladium/PC-Phos-catalyzed asymmetric Heck/Tsuji-Trost reaction was reported for the synthesis of various functionalized chiral hexahydroindoles with good yields and high enantioselectivity. The application of this reaction to the concise synthesis of (-)-alpha-Lycorane was demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Regina M. Oechsner, Ivo H. Lindenmaier, Ivana Fleischer
Summary: We present a nickel catalyzed C-S cross-coupling reaction of aryl and alkenyl triflates with alkyl thiols. By using an air-stable nickel precatalyst, various thioethers could be synthesized under mild reaction conditions within a short reaction time. The reaction demonstrated a broad substrate scope, including pharmaceutically relevant compounds.
Article
Chemistry, Multidisciplinary
Zi-Hao Chen, Rui-Ze Sun, Fei Yao, Xu-Dong Hu, Long-Xue Xiang, Hengjiang Cong, Wen-Bo Liu
Summary: The study presents an enantioselective nickel-catalyzed intramolecular reductive cross-coupling reaction to assemble CN-containing all-carbon quaternary stereocenters by desymmetrizing cyclization of aryl/alkenyl halide-tethered malononitriles. The use of an organic reductant is crucial for the selectivity and reactivity, with demonstrated applications in the synthesis of bioactive molecules and natural products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Jin-He Na, Xiang Liu, Jia-Wen Jing, Jing Wang, Xue-Qiang Chu, Mengtao Ma, Hao Xu, Xiaocong Zhou, Zhi-Liang Shen
Summary: A step-economical and efficient one-pot reaction was developed for the direct cross-coupling of aryl fluorosulfate with aryl bromide. This reaction, conducted at room temperature in THF solvent, does not require the use of preprepared/commercial organometallic reagents. By utilizing nickel catalyst, magnesium turnings, and lithium chloride, the desired biaryls were obtained in moderate to good yields with reasonable functional group compatibility.
Article
Chemistry, Organic
Michael Schrempp, Raphael Wagner, Hermann Gleich, Andreas Gansaeuer, Dirk Menche
Summary: A versatile titanocene-catalyzed radical allyl transfer reaction on epoxides has been reported, which enables efficient coupling of variously substituted allyl sulfones and the formation of quaternary carbon centers, providing a convenient method for further organic synthesis.
Article
Chemistry, Multidisciplinary
Anthony Lenormand, Lucia Reyes Mendez, Julien Coulomb
Summary: Unactivated alkenyl iodides and bromides underwent a palladium-catalyzed relay-Heck cross-coupling with alkenols to afford unsaturated aldehydes and ketones in moderate to good yields, while alkenyl triflates were not suitable partners for this reaction. This method allowed the preparation of open-chain analogues of the musk odorant Vulcanolide, some of which retained key olfactory properties of the parent molecule.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Qiaoli Li, Lanting Xu, Dawei Ma
Summary: Direct N-arylation of sulfonamides using a combination of copper and oxalamides (or 4-hydroxypicolinamides) as catalysts is an efficient method. It allows for a wide range of reactions between sulfonamides and (hetero)aryl bromides, and even works well with primary sulfonamides and (hetero)aryl chlorides under the catalysis of Cu2O and a 4-hydroxypicolinamide.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Lei Zhao, Xiao Meng, Yifeng Zou, Junsong Zhao, Lili Wang, Lanlan Zhang, Chao Wang
Summary: This report describes an intermolecular syn-arylalkylation and alkenylalkylation of alkenyl amines with two different organohalides using a Ni(II) catalyst. By utilizing cleavable bidentate quinolinamide, the reaction enables olefin difunctionalization with high levels of regio-, chemo-, and diastereocontrol, providing rapid access to branched aliphatic amines with high diastereoselectivities.
Article
Chemistry, Multidisciplinary
Xuan Jiang, Hao Jiang, Qian Yang, Ying Cheng, Liang-Qiu Lu, Jon A. Tunge, Wen-Jing Xiao
Summary: Grignard addition is an important method for synthesizing alcohol compounds, and the cobalt-catalyzed asymmetric reductive Grignard-type addition allows for the synthesis of chiral benzyl alcohols. This method has the advantages of mild reaction conditions, good functionality tolerance, and excellent enantiocontrol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Peizhuo Lv, Ali Wang, Xin Xie, Yulong Chen, Yuanhong Liu
Summary: An efficient method for the coupling of allyl trifluoroborates with aryl halides has been developed. The method offers high efficiency, mild reaction conditions, wide substrate scope, and functional group compatibility. Mechanistic studies suggest the formation of a pi-allyl nickel(III) intermediate as a key reaction intermediate.
Article
Chemistry, Organic
Guo-Qin Hu, Wen-Yan Zhang, Yong-Xin Liu, Jing-Hui Liu, Bin Zhao
Summary: Here, we present a decarboxylative thiocarbonylation method of aryl and alkenyl sulfonium salts using oxalic acid monothioethers (OAMs) under visible light-accelerated palladium catalysis. The reaction demonstrates a new application of visible light-accelerated palladium catalysis in catalytic decarboxylative cross-couplings, allowing the synthesis of different types of thioester compounds. Both sulfonium salts and OAMs are easily accessible and stored reagents.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Weiqi Liu, Xinghao Jin, Dawei Ma
Summary: The requirement of higher reaction temperatures for SNAr reaction between thiols and less reactive electron-poor aryl halides has led to the development of metal- and photo-catalyzed methods. In this study, the SNAr reaction between thiols and most electron-poor aryl halides was found to occur at RT-60°C using K2CO3 and DMAc. Additionally, two oxalic diamide ligands were identified to enable Cu-catalyzed coupling reactions with low catalytic loadings for unreactive (hetero)aryl halides, offering a promising approach for preparing (hetero)aryl thioethers.
Article
Chemistry, Organic
Yanling Zhang, Zhiguo Zhang, Yuanyuan Hu, Yunkui Liu, Hongwei Jin, Bingwei Zhou
Summary: We have described a nickel-catalyzed cyanation reaction of aryl/alkenyl halides with alkyl isocyanides. Aryl/alkenyl iodines and bromides were found to be competent electrophiles that reacted with alkyl isocyanides to afford nitrile compounds in moderate to good yields. This protocol features broad functional group tolerance, simple reaction conditions, and gram-scale synthesis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
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
Koki Kise, Shota Ooi, Hayate Saito, Hideki Yorimitsu, Atsuhiro Osuka, Takayuki Tanaka
Summary: Peripherally pi-extended corannulenes with quintuple azahelicene units were prepared and their dynamic behaviors were studied. Analysis revealed that the structural isomers can interchange in solution, depending on steric congestion, and the co-existing moieties influence the conformational dynamics, reducing activation energy barriers for isomerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Qian Zhang, Shijun Deng, Dong Li, Jun Shimokawa, Hideki Yorimitsu
Summary: A facile and efficient AgF-mediated electrophilic amination of alkoxyarylsilanes with azodicarboxylates has been developed. The reaction proceeds under green and mild conditions, generating aryl hydrazines.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Kazuhira Miwa, Shinobu Aoyagi, Takahiro Sasamori, Shogo Morisako, Hiroshi Ueno, Yutaka Matsuo, Hideki Yorimitsu
Summary: The reduction of fullerene (C-60) with sodium dispersion in the presence of an excess amount of dipropyl sulfate yields highly propylated fullerene, C-60(nC(3)H(7))(n) (max. n = 24), with C-60(nC(3)H(7))(20) being predominantly generated as indicated by mass spectrometry.
Article
Chemistry, Organic
Shuo Wang, Atsushi Kaga, Takashi Kurogi, Hideki Yorimitsu
Summary: In this study, treatment of arylcyclopropanecarboxamides with a sodium dispersion in the presence of methoxypinacolborane as a reduction-resistant electrophile was investigated. The results showed that the reaction led to the reductive cleavage of the cyclopropane ring followed by instant trapping with the boron electrophile, resulting in the formation of enolates of gamma-aryl-gamma-borylalkanamides. The enolates could further react with a different electrophile to produce the corresponding a-substituted amides with anti selectivity.
Article
Chemistry, Multidisciplinary
Gregory J. P. Perry, Hideki Yorimitsu
Summary: This Perspective discusses the use of sulfur(IV) compounds in transition-metal-free cross-coupling reactions and highlights the versatile reactivity of sulfur(IV) in designing new reagents, mediators, and catalysts.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Organic
Shunsuke Koyama, Fumiya Takahashi, Hayate Saito, Hideki Yorimitsu
Summary: Treatment of alkenyl carbamates with sodium dispersion and a co-existing boron electrophile leads to the formation of alkenylboronates through the reductive cleavage of the vinylic C-O bond, facilitated by the instant trapping of reactive organosodium species.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Shuo Wang, Igor Larrosa, Hideki Yorimitsu, Gregory J. P. Perry
Summary: The potassium salts of carboxylic acids are developed as efficient carboxylating agents through CO2 exchange. These carboxylates function as a combined source of CO2 and base/metalating agent, making them dual-function reagents. By using the salt of a commercially available carboxylic acid, this protocol provides a convenient and practical alternative to using CO2 gas or organometallic reagents, without the need for pressurized containers or strictly inert conditions. The reaction is mild, transition metal-free, and exhibits a wide range of substrate compatibility. The strategy showcased the ability to isotopically label biologically important molecules using low amounts of labeled CO2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Fumiya Takahashi, Hideki Yorimitsu
Summary: In this study, regio- and stereoselective synthesis of Tetraarylethylenes (TAEs) was achieved through sodium-promoted reductive anti-1,2-dimagnesiation of alkynes and palladium-catalyzed arylation. This method not only enables the synthesis of diarylacetylenes, but also allows for the synthesis of alkyl aryl acetylenes, expanding the range of possible TAEs.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Kazuhira Miwa, Shinobu Aoyagi, Toru Amaya, Takahiro Sasamori, Shogo Morisako, Takashi Kurogi, Hideki Yorimitsu
Summary: The curved and π-conjugated surface of bowl-shaped corannulene has been multiply methylated through in-situ iterative reduction/methylation sequences, resulting in exo-di-, -tetra-, and -hexamethylated corannulenes. Various analytical techniques have been used to reveal the molecular structures of the multimethylated corannulenes and the sequence of the multimethylation. This work has the potential to contribute to the controlled synthesis and characterization of multifunctionalized fullerenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Tomohiko Sato, Somnath N. Karad, Jun Shimokawa, Hideki Yorimitsu
Summary: The regioselective anti-silyllithiation of propargylic amines provides an efficient route for the synthesis of alkenylsilanes. The reaction involves the formation of a stable alkenyllithium intermediate through intramolecular coordination of the nitrogen functional group. After treatment with an electrophile, the alkenyllithium intermediate is functionalized to yield tetrasubstituted allylic amines bearing a beta-silicon substituent.
Article
Chemistry, Physical
Hiroki Yamagishi, Jun Shimokawa, Hideki Yorimitsu
Summary: The multifaceted implementation of silanols in organic synthesis is reviewed in terms of advances in transition metal-catalyzed reactions. The major properties of silanols are summarized, including their use as nucleophiles to serve as bulky surrogates for water, as temporary ligands to control the regioselectivity of metal-catalyzed reactions, and as coupling partners for transferring functional groups. These summaries provide opportunities for future developments in silanol chemistry.
Article
Chemistry, Organic
Ziwei Zhang, Fumiya Takahashi, Takashi Kurogi, Hideki Yorimitsu
Summary: The preparation of vinylic lithium reagents from vinylic halides is common in organic synthesis, but not always easy. This study proposes a new method using silyl enolates of alkyl aryl ketones, which provides readily available and efficient vinylic lithium species. The reductive transformation of electron-rich silyl enolates has significant potential for various applications in organic synthesis, serving as an alternative to the Shapiro reaction.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Sara Suzuki, Soni Aman Govind, Kosuke Imamura, Hideki Yorimitsu, Hiroshi Shinokubo, Masahiro Higashi, Hirofumi Sato
Summary: The radical cyclization reaction in aqueous environment by Yorimitsu et al. was reexamined using the RISM-SCF-cSED method, a hybrid approach combining quantum chemistry and statistical mechanics for molecular liquids. The difference in barrier height between the forward reaction from the intermediate E-rot, the cyclization step, and the backward reaction is crucial for the reaction yield. By considering the effect of hydrogen bonding through the RISM theory, it was found that the barrier height for the forward reaction is lower, particularly in water. In other words, accounting for microscopic solvation effects clearly elucidates the disparity between water and DMSO solvents, explaining the significant acceleration of the reaction in the aqueous environment.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Yiyuan Jiang, Hideki Yorimitsu
Summary: This study demonstrates the efficient generation of 1,4-organodilithiums through the reduction of styrenes with lithium arenide in flow microreactors. The use of a flow reactor with fast mixing is essential for achieving high efficiency and selectivity, which are low under batch conditions. The resulting 1,4-organodilithiums can react with various electrophiles to yield precursors for useful yet less accessible cyclic structures.
Article
Chemistry, Multidisciplinary
Hiroki Yamagishi, Kenshiro Hitoshio, Jun Shimokawa, Hideki Yorimitsu
Summary: This study extends the utility of sodium silylsilanolates as competent precursors of silylcoppers, and the mechanistic studies through DFT calculation reveal the mechanism of copper silylsilanolate transforming into silylcopper.