Article
Chemistry, Organic
Lin Li, Xin-Lian Liu, Jin-Yan Liang, Yong-Yu He, Ai-Jun Ma, Wei-Feng Wang, Jin-Bao Peng
Summary: A palladium-catalyzed dicarbonylation reaction of alpha-iodo-substituted ACPs has been developed for the synthesis of carbamoyl-substituted indenones. Two carbonyl groups are incorporated into the product by cleaving the proximal C-C bond of the ACPs. A broad range of carbamoyl-substituted indenones are efficiently prepared with good to excellent yields.
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, Organic
Peng Wang, Ji Yang, Kangkang Sun, Helfried Neumann, Matthias Beller
Summary: The direct palladium-catalyzed selective carbonylative coupling of less reactive aryl chlorides with primary and secondary amines is achieved using a palladium/Xantphos catalyst system and cesium chloride as an additive. This reaction shows high conversion for various aryl chlorides and good functional group compatibility.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Organic
Lucie Finck, Martin Oestreich
Summary: This perspective provides an overview of the underexplored chemistry of diazenes and highlights their potential in synthetic transformations. The stability and reactivity of diazenes have been enhanced by using silicon protection. The generation of aryl, diazenyl, and alkyl anionic intermediates under catalytic conditions opens up new synthetic approaches as alternatives to existing methodologies.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Lars J. Wesenberg, Alessandra Sivo, Gianvito Vile, Timothy Noel
Summary: In recent years, there has been a trend in the synthetic community to introduce sp(3)-carbon-based fragments in organic compounds through cross-coupling strategies. This study presents a novel nickel-catalyzed electrochemical methodology for reductive cross-electrophile coupling, using inexpensive amine-derived radical precursors and aryl iodides. The use of electrochemistry as a power source reduces waste and avoids chemical reductants, making this approach a more sustainable alternative to traditional cross-coupling methods.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Rudolfs Belaunieks, Mikus Purins, Rebeka Anna Lipina, Anatoly Mishnev, Maris Turks
Summary: This study focuses on the activation of terminal alkynes with a silyl group and the synthesis of stereochemically defined allyl ethers and esters through 1,2-silyl group migration and interception reactions with external nucleophiles. The obtained products can serve as building blocks for further functionalization reactions.
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, Multidisciplinary
Mengfu Dai, Zhimin Sun, Liang-An Chen
Summary: This study reports a catalyst-controlled, tunable, and predictable regiodivergency in transforming internal aliphatic propargyl esters into diverse products, allowing facile access to regioisomers with high regio- and stereoselectivity. This method is important for the structural diversification of bioactive molecules, enabling the rapid assembly of structural analogs of pharmaceutical candidates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Lisa Marie Kammer, Shorouk O. Badir, Ren-Ming Hu, Gary A. Molander
Summary: A dual photochemical/nickel-mediated decarboxylative strategy for the assembly of C(sp(3))-C(sp(2)) linkages has been developed. This platform utilizes commercially available Hantzsch ester as an organic photoreductant to generate catalytically active Ni(0) species under light irradiation, enabling the coupling of diverse C(sp(3))-centered radical architectures with (hetero)aryl bromides. The protocol proceeds under mild reaction conditions and is compatible with sensitive functional groups and pharmaceutically relevant cores.
Article
Chemistry, Multidisciplinary
Kenshiro Hitoshio, Hiroki Yamagishi, Jun Shimokawa, Hideki Yorimitsu
Summary: A diverse range of aryl chlorides underwent silylation using sodium silylsilanolate reagents in the presence of a Ni(cod)(2) catalyst complexed with phosphine ligands. The reaction conditions were mild and allowed for silylation of various aryl chlorides, including functionalised drug molecules.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Kazuki Tomota, Yuki Izumi, Kazuki Nakanishi, Masaaki Nakamoto, Hiroto Yoshida
Summary: A direct and transition metal-free method for the installation of B(dan) into organic frameworks has been developed. Heteroaryl-H bonds can be transformed into heteroaryl-B(dan) bonds through deprotonation. The resulting heteroaryl-B(dan) compounds, which are typically difficult to access, can undergo direct Suzuki-Miyaura coupling. The method has also been demonstrated to be applicable to silicon nucleophiles, leading to the formation of Lewis acidity-diminished stable silyl-B(dan) and -B(aam) in one pot.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Sheng Zhang, Wenchao Gao, Jianxue Shi, Jingjing Li, Fengyi Li, Yating Liang, Xuan Zhan, Man-Bo Li
Summary: An umpolung addition of dicyanobenzene to alpha,beta-unsaturated alkenes has been developed using an electroreductive strategy. The electrochemical protocol is compatible with challenging substrates, and good regioselectivities are observed in the reaction. The synthetic utility of this electrochemical approach is demonstrated by direct functionalization of two compounds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Tom J. M. Byrne, Megan E. Mylrea, James D. Cuthbertson
Summary: This article describes a simple and efficient strategy for synthesizing substituted tetrahydrofurans from readily available cis-butene-1,4-diol. A redox-relay Heck reaction is used to quickly obtain cyclic hemiacetals, which can be directly reduced to obtain the corresponding 3-aryl tetrahydrofuran. Furthermore, these hemiacetals can also serve as precursors to a variety of disubstituted tetrahydrofurans, including the calyxolane natural products.
Article
Chemistry, Organic
Jakkula Naveen, Gedu Satyanarayana
Summary: In this study, an efficient and versatile method for [3+2] annulation of ortho-substituted iodoarenes with maleimides via a palladium-catalyzed consecutive double Heck-type strategy was reported, leading to fused tricyclic frameworks of pharmaceutical relevance.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Chen Chen, Liying Liu, Jin-Ping Liu, Jie Ding, Chang Ni, Chunjie Ni, Bolin Zhu
Summary: We describe a palladium-catalyzed Heck-carbonylation reaction of alkene-tethered carbamoyl chlorides using aryl formates as convenient CO surrogates. This reaction allows for the construction of one C-O and two C-C bonds, resulting in the formation of diverse esterified oxindoles and γ-lactams with an all-carbon quaternary stereocenter under gas-free conditions. This transformation exhibits a broad substrate scope, excellent functional group tolerance, and can be readily applied for late-stage functionalization.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
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.