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, Physical
Florian Papp, Daniel Sowa Prendes, Sourav Manna, Ann-Katrin Seitz, Sofiya Kostiukovska, Julian Loeffler, Viktoria H. Gessner, Lukas J. Goossen
Summary: Palladium complexes with ylide-functionalized phosphine ligands catalyze the arylation of N-protected hydantoins with aryl chlorides, enabling the synthesis of a wide variety of hydantoins, including derivatives of the anticonvulsant drugs phenytoin and mephenytoin. Selective monoarylations, sequential diarylations, and arylation-alkylation sequences have been achieved, along with stepwise deprotection strategies.
Article
Chemistry, Multidisciplinary
Daniel Sowa Prendes, Florian Papp, Nagesh Sankaran, Nardana Sivendran, Frederike Beyer, Christian Merten, Lukas J. Goossen
Summary: Arylglycines, which are important pharmacophores in several top-selling drugs, can now be synthesized from abundant aryl chlorides using a Pd-catalyzed Schollkopf-type amino acid synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ren-Xiao Liang, Chao Zhong, Zhi-Hong Liu, Miao Yang, Heng-Wei Tang, Jian-Fei Chen, Yun-Fang Yang, Yi-Xia Jia
Summary: Palladium-catalyzed intramolecular enantioselective beta-arylation of tetrasubstituted endocyclic and exocyclic enamines can lead to a range of optically active products with high enantiomeric ratios. Different bases and chiral ligands can be used to achieve different levels of enantioselectivity.
Article
Chemistry, Multidisciplinary
Xin Liu, Yun Zhou, Xiaotian Qi, Renhe Li, Peng Liu, Guangbin Dong
Summary: A site- and regioselective vicinal di-carbo-functionalization of indoles has been realized by the palladium/norbornene (Pd/NBE) cooperative catalysis. The C1-substituted NBE plays a key role in promoting the turnover-limiting oxidative addition step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Bingxiang Xue, Jie Shen, Sourav Manna, Angelino Doppiu, Lukas J. Goossen
Summary: A new catalyst has been discovered that can selectively introduce a primary amino group into aromatic compounds, and it can efficiently promote the amination reaction to synthesize primary anilines within 30 minutes.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Sanliang Li, Qiaoyu Chen, Junfeng Yang, Junliang Zhang
Summary: In this study, an efficient asymmetric gamma-arylation method for constructing chiral quaternary arylated butenolide was reported. The method showed high selectivity, good functional group tolerance, and excellent enantioselectivity. Additionally, it allowed for the facile construction of tricyclic tetrahydroindolines and tetrahydroisoquinolinones in one step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Adrian Tlahuext-Aca, Sarah Yunmi Lee, Shu Sakamoto, John F. Hartwig
Summary: A new method for the direct catalytic arylation of simple arenes using aryl bromides is described. The method does not rely on directing groups and instead utilizes a synergistic catalytic cycle involving phosphine-ligated silver complexes and palladium catalysts. Mechanistic experiments indicate that cleavage of the C-H bond by silver is the rate-determining step in the catalytic cycle.
Review
Biochemistry & Molecular Biology
Garazi Urgoitia, Maria Teresa Herrero, Fatima Churruca, Nerea Conde, Raul SanMartin
Summary: Direct arylation is an atom-economical alternative to established procedures, and the use of palladium pincer complexes as catalysts has led to improved efficiency and reaction yields. This paper reviews intra- and intermolecular direct arylation reactions and discusses the role of these active catalysts.
Article
Chemistry, Organic
Kyohei Yonekura, Mari Murooka, Kohei Aoki, Eiji Shirakawa
Summary: The electrochemical a-arylation of alkylamines with sulfonylarenes has been developed, allowing for the synthesis of a variety of a-arylalkylamines. Mechanistic studies demonstrate that anodic oxidation of an alkylamine with a sulfinate as a mediator followed by deprotonation produces an a-aminoalkyl radical, which undergoes homolytic aromatic substitution on a sulfonylarene, giving the corresponding a-arylalkylamine.
Article
Chemistry, Organic
Haoran Li, Hai-Yun Huang, Thierry Roisnel, Henri Doucet
Summary: This method describes the regioselective palladium-catalyzed direct arylation of 6,7-difluorobenzo[d]imidazole using aryl bromides as coupling partners, with a preference for the C2-carbon of the difluorobenzo[d]imidazole. It tolerates a variety of substituents at different positions on the aryl bromide, as well as N-containing heteroaryl bromides.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Milos Petkovic, Milos Jovanovic, Predrag Jovanovic, Milena Simic, Gordana Tasic, Vladimir Savic
Summary: Pyrrole derivatives with C(2)-aryl substituents are an important and widespread class of heterocyclic compounds. A novel approach combining the dual role of arylating agent as nitrogen protecting group and involved in the arylation step has been developed for the direct arylation synthesis of C(2)-arylpyrroles. The deprotection as a final stage is carried out simultaneously utilizing amines as reacting components, leading to mild conditions and exclusive C(2) selectivity.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Oumaima Mhadhbi, Linhao Liu, Amal Benzai, Besma Mellah, Neji Besbes, Jerome Ollivier, Marie Cordier, Henri Doucet
Summary: The regioselectivity of Pd-catalyzed direct arylation of unsubstituted 2-alkylisothiazol-3(2H)-ones was investigated and conditions for the regioselective palladium-catalyzed direct C5-arylation of 2-alkylisothiazol-3-ones using aryl bromides were reported. This method tolerates a wide variety of substituents on the aryl bromide and allows for the synthesis of diverse isothiazolinone derivatives.
Article
Chemistry, Applied
Atul Dubey, Neha Singh Chauhan, Zanjila Azeem, Pintu Kumar Mandal
Summary: A Pd(II)-catalyzed, bidentate directing group (BDG)-assisted C(sp(2))-H functionalization of C2-amido glycals onto the anomeric position is reported as a contemporary approach for the synthesis of various unsymmetrical gem-diarylmethyl C-glycosides. The use of a bidentate amidoquinoline-type directing group enables the insertion of different para-quinone methides (p-QMs) onto the pseudo-anomeric position of glycal substrates, yielding moderate to good yields. The final product can be further functionalized through known palladium-catalyzed cross-coupling reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
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, Multidisciplinary
Shuhei Akahori, Atsushi Kaga, Jinseok Kim, Hideki Yorimitsu, Dongho Kim, Hiroshi Shinokubo, Yoshihiro Miyake
Summary: In this study, C-4h-symmetric octaaza[8]circulenes were synthesized and exhibited enhanced antiaromaticity upon protonation. The protonation of the pyridine rings enhanced the contribution of the octaaza[8]circulenes' antiaromatic character.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Akito Nakai, Hayate Saito, Hideki Yorimitsu, Takayuki Tanaka, Atsuhiro Osuka
Summary: A meso-free beta-bromodecaphyrin and a beta-unsubstituted meso-free [46]decaphyrin were synthesized. The [46]decaphyrin exhibits distinct aromaticity and flexible conformational change.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Kodai Yamada, Mika B. Kintzel, Gregory J. P. Perry, Hayate Saito, Hideki Yorimitsu
Summary: The formation of zinc reagents by the reaction of styrylsulfonium salts with zinc powder is reported, without the need for transition metals or other additives. The method shows good tolerance towards a variety of sensitive functional groups and can be used in various functionalizations.
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
Zhouen Zhang, Takashi Niwa, Kenji Watanabe, Takamitsu Hosoya
Summary: In this study, a two-phase radiosynthetic method for the ipso-C-11-cyanation of aryl fluorides was developed, using nickel-mediated C-F bond activation. A practical protocol was established that does not require a glovebox, making it applicable for general PET centers. This method enabled the efficient synthesis of diverse [C-11]aryl nitriles, including pharmaceutical drugs. Stoichiometric reactions and theoretical studies demonstrated the significant promotion effect of lithium chloride on the oxidative addition, facilitating rapid C-11-cyanation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Takashi Niwa, Tsuyoshi Tahara, Charles E. Chase, Francis G. Fang, Takayoshi Nakaoka, Satsuki Irie, Emi Hayashinaka, Yasuhiro Wada, Hidefumi Mukai, Kenkichi Masutomi, Yasuyoshi Watanabe, Yilong Cui, Takamitsu Hosoya
Summary: This study reports the successful 11C-radiolabeling of eribulin, an approved anticancer drug, which enables the quantitative measurement of eribulin migration into tumor tissue. The optimized synthetic method provides a reproducible way to produce [35-11C]eribulin with high radiochemical purity and molar activity. PET imaging using mice shows specific accumulation of [35-11C]eribulin in tumors without significant metabolic changes.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(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
Psychiatry
Manon Dubol, Jana Immenschuh, My Jonasson, Kayo Takahashi, Takashi Niwa, Takamitsu Hosoya, Sara Roslin, Johan Wikstrom, Gunnar Antoni, Yasuyoshi Watanabe, Mark Lubberink, Anat Biegon, Inger Sundstrom-Poromaa, Erika Comasco
Summary: The study investigated the availability of aromatase in healthy women before and after nicotine exposure. The findings suggest that nicotine acutely decreases aromatase availability in the thalamic area, indicating a potential mechanism mediating the effects of nicotine on human behavior.
COMPREHENSIVE PSYCHIATRY
(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, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
