Review
Chemistry, Organic
Zhang Jian, Chen Ying, Wang Quannan, Shen Jiahuan, Liu Yangzi, Deng Weiping
Summary: The article introduces the asymmetric synthesis of chiral heterocyclic compounds using transition metal-catalyzed cyclization, focusing on the application and issues of allyl or propargyl heteroatom-dipole precursors.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Martin Pineiro-Suarez, Andres M. Alvarez-Constantin, Martin Fananas-Mastral
Summary: A catalytic asymmetric reaction involving allyl copper species with allylic gem-dichloride is reported, providing high selectivity chiral internal 1,5-dienes with (Z)-configured alkenyl boronate and alkenyl chloride. The synthetic utility of the products is demonstrated by synthesizing optically active compounds. DFT calculations reveal noncovalent substrate-ligand interactions accounting for the selectivity outcome.
Article
Chemistry, Multidisciplinary
Mingxin Liu, Nguyen Le, Christopher Uyeda
Summary: Nickel catalysts promote nucleophilic cyclopropanation reactions using CH2Cl2 as a methylene source and Mn as a stoichiometric reductant. The substrate scope includes a broad range of alkenes bearing electron-withdrawing substituents, and enantioselective cyclopropanations have been developed using chiral PyBox ligands. Mechanistic studies suggest the intermediacy of a (PyBox)Ni=CH2 species and DFT models provide a rationale for the nucleophilic character of the nickel carbene and the sense of enantioinduction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Johannes Grosskopf, Thorsten Bach
Summary: Upon irradiation with a suitable chiral catalyst, racemic compounds can be converted into enantiopure compounds through a process called photochemical deracemization. This review comprehensively covers the research and current developments in this field, discussing the reactions and mechanistic details underlying the presented reaction. Photochemical deracemization offers a unique opportunity to directly obtain enantiopure compounds from racemates, and short-lived intermediates play a key role in determining the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhenhua Zhang, Julius B. Stueckrath, Stefan Grimme, Andreas Gansaeuer
Summary: Cp2Ti(TFA) is a versatile catalyst for the [2+2] cycloaddition of bisenones through inner-sphere electron transfer, with a unique 5-exo step as the rate-determining step followed by a favorable 4-exo cyclization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jiangyan Tian, Wendian Li, Ruihao Li, Lin He, Hui Lv
Summary: The nickel/(S)-t-Bu-PHOX complex catalyzed asymmetric arylative cyclization of N-alkynones has successfully delivered 1,2,3,6-tetrahydropyridines containing a chiral tertiary alcohol in high yields and excellent enantioselectivities, providing efficient access to chiral tetrahydropyridine and piperidine analogues.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Oliver D. Jackson, Ksenia S. Stankevich, Matthew J. Cook
Summary: An auto-tandem catalytic, branched-selective rearrangement of substituted N-alloc-N-allyl ynamides was developed, which provides an easy access to complex quaternary nitrile products with vinylogous stereocentres in excellent diastereoselectivity, including contiguous all-carbon quaternary centres. The stereochemical outcome is determined via a Pd(0) catalysed dipolar ketenimine aza-Claisen rearrangement, and computational studies illustrate the significant role of ligand geometry.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Jessica Rodriguez, David Vesseur, Alexis Tabey, Sonia Mallet-Ladeira, Karinne Miqueu, Didier Bourissou
Summary: A (MeDalphos)AuCI complex has been discovered to efficiently catalyze the cross-coupling reaction of indoles and allyl acetates/alcohols. The reaction tolerates various functional groups and selectively produces branched C3-allylated products. It utilizes the hemilabile character of the P<^>N ligand.
Article
Chemistry, Applied
Irene Martin, Cristina Aragoncillo, Pedro Almendros
Summary: This research has achieved a selective palladium-catalyzed reaction sequence, leading to the synthesis of novel 2-iodo-1-aryl-9H-carbazoles. The observed formation of 2-iodocarbazoles in contrast to gold catalysis suggests a metal-controlled cyclization through chemo- and regioselective alkyl migration and iodonium migration.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Fabian Scharinger, Adam Mark Palvoelgyi, Melanie Weisz, Matthias Weil, Christian Stanetty, Michael Schnuerch, Katharina Bica-Schroeder
Summary: In this study, we propose a novel approach for various asymmetric transformations of cyclic enones. By optimizing the catalyst components, we have developed a particularly powerful and versatile organocatalyst that shows excellent stereocontrol. Furthermore, a simple change in the diamine's configuration allows access to both product antipodes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Marta Solas, Samuel Suarez-Pantiga, Roberto Sanz
Summary: This study describes the asymmetric synthesis of cyclopentachromenones from gold-catalyzed reaction of readily available skipped alkenynones. The cascade reaction involves an initial anti-Michael hydroarylation and a subsequent Nazarov cyclization. Excellent enantiomeric ratios and chemical yields are achieved under mild reaction conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shrikant D. Tambe, Cheol Hyeon Ka, Ho Seong Hwang, Jaehan Bae, Naeem Iqbal, Eun Jin Cho
Summary: The synthesis of highly functionalized chiral 3-pyrrolines is important for the production of natural and synthetic bioactive molecules. Previous methods using allenoates could not synthesize 3,4-disubstituted 3-pyrrolines. This study presents a novel approach to produce 2,3,4-trisubstituted chiral 3-pyrrolines through a highly stereoselective process using a Ni-II/Fc-i-PrPHOX catalytic system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Soumyadeep Chakrabortty, Shasha Zheng, Fabian Kallmeier, Eszter Barath, Sergey Tin, Johannes G. de Vries
Summary: A readily available chiral Ru/bisphosphine catalyst was used to achieve the direct asymmetric reductive amination of bio-based levulinic acid (LA) to produce enantioenriched 5-methylpyrrolidinone with excellent enantioselectivity (up to 96% ee) and high isolated yield (up to 89%). Methyl levulinate (ML), a byproduct from the industrial production of 2,5-furandicarboxylic acid (FDCA), can be used as a substitute for LA with similar reactivity and selectivity. Mass spectrometry and isotope labelling studies suggest that the chiral lactam is formed through imine-enamine tautomerization/cyclization followed by asymmetric hydrogenation of the cyclic enamide.
Article
Chemistry, Multidisciplinary
Harley Green, Stephen P. Argent, Hon Wai Lam
Summary: This study describes a novel domino reaction involving nickel-catalyzed additions of (hetero)arylboronic acids to alkynes, followed by cyclization onto acyclic ketones to yield chiral tertiary-alcohol-containing products with high enantioselectivities. The reversible E/Z isomerization of the alkenylnickel intermediates allows overall anti-arylmetallative cyclization to occur, producing products with ring systems similar to certain diarylindolizidine alkaloids.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Juan Du, Yun-Fan Li, Chang-Hua Ding
Summary: Palladium-catalyzed cycloaddition reactions using Pd-p-allyl zwitterions are significant synthetic transformations for the construction of carbon- or heterocycles compounds found in biologically active natural products and pharmaceuticals. Recent studies have explored new applications of previously less-studied Pd-p-allyl zwitterions and designed impressive novel zwitterions, which are diverse and highly reactive intermediates for the synthesis of complex polycyclics and medium-sized cyclic compounds.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Organic
Toshifumi Takeuchi, Naoya Kumagai, Masakatsu Shibasaki
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
Bo Sun, Roman Pluta, Naoya Kumagai, Masakatsu Shibasaki
Article
Chemistry, Organic
Zhongdong Sun, Bo Sun, Naoya Kumagai, Masakatsu Shibasaki
Article
Chemistry, Organic
Zijian Liu, Hidetoshi Noda, Masakatsu Shibasaki, Naoya Kumagai
Article
Chemistry, Organic
Zhao Li, Hidetoshi Noda, Naoya Kumagai, Masakatsu Shibasaki
Article
Chemistry, Organic
Yohei Matsumoto, Taro Tsuji, Daiki Nakatake, Ryo Yazaki, Takashi Ohshima
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Ryo Yazaki, Takashi Ohshima
TETRAHEDRON LETTERS
(2019)
Article
Chemistry, Multidisciplinary
Tsukushi Tanaka, Ryo Yazaki, Takashi Ohshima
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Yohei Matsumoto, Jun Sawamura, Yumi Murata, Takashi Nishikata, Ryo Yazaki, Takashi Ohshima
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Organic
Taro Tsuji, Takafumi Tanaka, Tsukushi Tanaka, Ryo Yazaki, Takashi Ohshima
Review
Chemistry, Medicinal
Ryo Yazaki
Summary: The described catalytic chemoselective reactions enable selective activation of less reactive functionalities over more reactive ones, allowing for efficient synthesis of complex molecules without the need for tedious protection-deprotection processes. This offers new opportunities for innovative drug discovery research by expanding the chemical space available for exploration.
CHEMICAL & PHARMACEUTICAL BULLETIN
(2021)
Article
Chemistry, Organic
Tetsu Ikeda, Haruka Ochiishi, Mana Yoshida, Ryo Yazaki, Takashi Ohshima
Summary: This method involves the synthesis of a highly congested alpha,beta-dehydroamino acid through the beta-C-H bond activation of an amino acid Schiff base, with the use of abundant hydrocarbon feedstock as an alkylating reagent. The resulting alpha,beta-dehydroamino acid bears a quaternary carbon at the gamma-position with an exclusively (Z)-geometry. Additionally, a tetrasubstituted olefin can be constructed from saturated starting materials, and the synthesis also allows for the transformation into unnatural alpha-amino acid derivatives.
Article
Oncology
Kazumasa Yoshida, Kensuke Nishi, Shuhei Ishikura, Kazuhiko Nakabayashi, Ryo Yazaki, Takashi Ohshima, Masahiko Suenaga, Senji Shirasawa, Tosiyuki Tsunoda
Summary: The study discovered that NPD10621 and its derivatives can selectively suppress the growth of cancer spheroids with mutant KRAS. Among these derivatives, PMC showed the most effective inhibition of mutant KRAS spheroid growth with the least toxicity. Furthermore, PMC was able to suppress the growth of various cancer cell lines, indicating its context-independent role in cancer growth.
ANTICANCER RESEARCH
(2022)
Article
Oncology
Kazumasa Yoshida, Kensuke Nishi, Shuhei Ishikura, Taichi Matsumoto, Kazuhiko Nakabayashi, Ryo Yazaki, Takashi Ohshima, Masahiko Suenaga, Senji Shirasawa, Toshiyuki Tsunoda
Summary: In this study, RNA-seq analyses were conducted to investigate the mechanism of PMC against human colorectal cancer cells with mtKRAS. The results showed that PMC suppresses the aerobic glycolysis pathway through down-regulation of the HIF1 pathway, leading to the inhibition of cancer growth.
ANTICANCER RESEARCH
(2023)
Review
Chemistry, Organic
Tsukushi Tanaka, Ryo Yazaki, Takashi Ohshima
Summary: Enolization of carboxylic acid derivatives is a challenging task due to the low acidity of alpha-protons, requiring strong bases for efficient activation. Recent developments in catalytic methods have shown potential for chemoselective activation of carboxylic acids through a radical process, allowing for concise synthesis of diverse unnatural derivatives.
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2021)
