Article
Chemistry, Applied
Yuan He, Zilong Huang, Juan Ma, Jie Lin, Yong-Gui Zhou, Zhengkun Yu
Summary: A transition-metal-free method was developed for the cleavage of C-H bonds in olefins. By using vinylsulfonium salts and sodium azide, sulfanyl-azidoalkene compounds were synthesized and further transformed into various derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Ze-Yu Tian, Zeng-Hui Lin, Cheng-Pan Zhang
Summary: A selective formal C-H/C-H cross-coupling of azoles and (hetero)arenes was established using arylsulfonium intermediates under transition-metal catalysis, providing a variety of 2-(hetero)aryl azoles in good to excellent yields. The advantages of this reaction include mild reaction conditions, good functional group tolerance, a wide substrate scope, high regio- and chemoselectivity, one-pot procedures, and late-stage functionalization of complex molecules without the use of oxidants, offering a promising strategy for transition-metal-catalyzed C-H arylation of azoles.
Article
Chemistry, Organic
Qiang Wang, Shuaijie Wu, Yi-Dong Wang, Jing Sun, Ying Han, Chao-Guo Yan, Lei Wang
Summary: Here, a new and efficient strategy for the synthesis of alkenyl sulfoxides is reported. The method involves the transition metal-free C-S cross-coupling reaction between sulfenate anions and alkenylsulfonium salts. The in situ generation of sulfenate anions from beta-sulfinyl esters under mild conditions provides an effective approach for the synthesis of diverse alkenyl sulfoxides in moderate to good yields.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Akash G. Tathe, Nitin T. Patil
Summary: This study reports C(sp(2))-S cross-coupling reactions of aryl iodides and arylsulfonyl hydrazides under ligand-enabled, Au(I)/Au(III) redox catalysis, highlighting the utility of this method for synthesizing various medicinally relevant biaryl sulfones without the need for prefunctionalized aryl coupling partners.
Article
Chemistry, Multidisciplinary
Fabio Julia, Jiyao Yan, Fritz Paulus, Tobias Ritter
Summary: A vinyl thianthrenium salt has been introduced as an effective vinylating reagent, which can be readily prepared from ethylene gas and is broadly useful in various annulation chemistry reactions. Its unique structural features enable a distinct synthesis and reactivity profile, unprecedented for other vinyl sulfonium derivatives.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Mengyu Gao, Corinne Gosmini
Summary: The cross-electrophilic coupling of various benzyl sulfonium salts with Callyl-O electrophiles is achieved using a Co-Mn catalytic system. This system activates the stable Csp(3)-S bond of sulfonium salts and the Csp(3)-O bond of allylic acetate or ether to produce diverse alkyl olefinic compounds under mild conditions. The use of allyl methyl ethers in transition metal-catalyzed cross-electrophilic coupling to form Csp(3)-Csp(3) bonds is reported for the first time. Preliminary mechanistic studies suggest the involvement of benzyl radicals generated through single electron transfer-mediated C-S bond cleavage.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Zeqi Jiang, Sheng-Li Niu, Qiang Zeng, Qin Ouyang, Ying-Chun Chen, Qing Xiao
Summary: A novel Pd-catalyzed reaction has been developed for selective alkynylallylation of specific C-C sigma bonds in cyclopropenes, providing an efficient approach to highly functionalized dienynes. The reaction features fascinating atom and step economy and can produce gram-scale products using a simple, neutral, and low-cost catalytic system with high TONs. DFT calculations suggest that the success of the reaction relies on the selective insertion of cyclopropene double bonds into the C-Pd bond of ambidentate Pd complex and subsequent nonclassical beta-C elimination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Weitao Yan, Mingwen Zheng, Peihsuan Chuang, Hao Sun, Shiping Wang, Chunfa Xu, Fen-Er Chen
Summary: A highly efficient coupling of glycosyl stannanes and sulfonium salts enabled by synergistic Pd/Cu catalysis has been developed for the construction of C-aryl/alkenyl glycals. This protocol demonstrates wide functional group tolerance and the one-pot formal C-H glycosylation starting from arene. Additionally, the successful gram-scale reaction indicates the high applicability of this method.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Organic
Weijie Yu, Juelin Wan, Puqing Chen, Kuang Zhao, Haijin Huang, Tao Wang, Jin Luo
Summary: A palladium-catalyzed cross-coupling reaction between benzene sulfonyl hydrazides and benzyltrimethylammonium salts via C-S and C-N bond cleavage has been reported. This reaction proceeds under mild conditions and provides a new strategy for the synthesis of various diarylmethanes with good functional group tolerance and moderate to good yields.
SYNTHETIC COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Ying Lin, Liang Zou, Renren Bai, Xiang-Yang Ye, Tian Xie, Yang Ye
Summary: We present an easy and efficient method for vinylation using Fe-catalyzed cross-electrophile coupling of readily available vinyl- and hydro-chlorosilanes with a range of substituted alkenyl bromides using manganese as the terminal reductant. This modular approach allows the formation of various vinyl orgaonosilanes, including electron-rich, electron-poor, and ortho-/meta-/para-substituted vinyl electrophiles, with excellent functional group tolerance and broad substrate scope. Furthermore, this method successfully modified substrates with structurally complex natural products and pharmaceutical motifs, demonstrating its potential in gram-scale reactions and derivatization.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Kangning Cao, Zhan-Ming Zhang, Junliang Zhang, Fener Chen
Summary: The study presents a highly selective Pd-catalyzed reaction for the synthesis of a series of chiral benzene-fused cyclic compounds in a convenient manner.
Review
Chemistry, Multidisciplinary
Massimo C. D'Alterio, Eric Casals-Cruanas, Nikolaos V. Tzouras, Giovanni Talarico, Steven P. Nolan, Albert Poater
Summary: The story of C-C bond formation involves various reactions, with Suzuki-Miyaura reaction being one of the most outstanding ones. The focus is on the formation of catalytically active species, with preactivation potentially playing a role as the rate determining step in the overall reaction. Computational chemistry plays a key role in identifying the rate determining step and achieving milder conditions in experimental settings through predictive catalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Che-Ming Hsu, Shao-Chi Lee, Hao-En Tsai, Yong-Ting Tsao, Cheng-Lin Chan, Shinje Minoza, Zong-Nan Tsai, Li-Yun Li, Hsuan-Hung Liao
Summary: In this study, we successfully activated the C-S bond in sp(3)-hybridized thiols by introducing a per-/polyfluoroaryl moiety, enabling the efficient removal of sulfur groups and the generation of aliphatic radicals that can react with aryl halides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Roberto del Rio-Rodriguez, Laura Blanco, Alba Collado, Jose A. Fernandez-Salas, Jose Aleman
Summary: In this study, a nickel-catalysed reductive cross-coupling reaction between benzyl sulfonium salts and benzyl bromides is reported. Simple, stable and readily available sulfonium salts have shown their ability as leaving groups in cross-electrophile coupling, allowing the formation of challenging sp(3)-sp(3) carbon-carbon bonds for the synthesis of interesting dihydrostilbene derivatives. Additionally, benzyl tosyl derivatives have been demonstrated to be suitable substrates for reductive cross-coupling by in-situ formation of the corresponding sulfonium salt.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Celine Dorval, Oleh Stetsiuk, Sylvaine Gaillard, Elodie Dubois, Corinne Gosmini, Gregory Danoun
Summary: A novel Negishi-type cross-coupling reaction using only cobalt bromide salt as the catalyst is described in this study. This original reaction demonstrates high tolerance to various glutarimide amides and organozinc coupling partners. Additionally, the reaction can be performed on a large scale using an eco-compatible solvent such as ethyl acetate.
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.