Article
Chemistry, Organic
Dawid J. Kucharski, Rafal Kowalczyk, Przemyslaw J. Boratynski
Summary: Novel 1,2-diamines based on the mefloquine scaffold were prepared, with the most effective 11-aminomefloquine obtained through conversion of the 11-alcohol and subsequent alkylation. The substitution reactions mostly retained the configuration, and enantiomerically pure products were obtained through resolution. The efficacy evaluation of the obtained vicinal diamines showed that erythro-11-aminomefloquine is a superior catalyst in asymmetric transformations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Ken Okuno, Bun Chan, Seiji Shirakawa
Summary: Catalytic kinetic resolution is a reliable method for enantioselective synthesis of chiral molecules. However, it is challenging to perform kinetic resolution on racemic compounds with similar substituents at a chiral center. In this study, a kinetic resolution of a-allyl-a-propargyl carboxylic acids was achieved using a chiral bifunctional sulfide catalyst. The utility of the resulting optically active compounds was also demonstrated.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ming-Yang Wang, Wei Li
Summary: Feng ligand, a conformationally flexible and C-2-symmetric privileged chiral ligand, has shown tremendous success in asymmetric catalysis, versatile coordination chemistry, and diverse areas of catalysis. Its ability to provide an excellent chiral environment challenges the conventional idea of rigid structures in chiral ligand design.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Jose A. Carmona, Carlos Rodriguez-Franco, Joaquin Lopez-Serrano, Abel Ros, Javier Iglesias-Siguenza, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An efficient dynamic kinetic resolution (DKR) approach has been developed for the synthesis of axially chiral diamines based on ruthenium-catalyzed enantioselective transfer hydrogenation. This method features a broad substrate scope and proceeds under very mild conditions, allowing the preparation of BINAM homologues in good to high yields and nearly perfect enantioselectivities (up to 99% ee).
Article
Chemistry, Organic
Paul Zebrowski, Uwe Monkowius, Mario Waser
Summary: We report a two-step approach for the enantioselective synthesis of novel chiral δ-lactams. The protocol involves an asymmetric α-allylation of activated aryl esters followed by an acid-mediated lactam formation. The method provides highly enantioselective and reasonably high-yielding products, which can be further utilized via transformations of the exocyclic double bond.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Caifang Han, Wei Meng, Xiangqing Feng, Haifeng Du
Summary: Asymmetric intramolecular hydroalkoxylation is an important method for accessing optically active cyclic ethers. The cyclization of 2-vinylbenzyl alcohols can be catalyzed by B(C6F5)3 with low catalyst loading, resulting in high yields. A novel chiral boro-phosphate was developed to achieve high enantioselective hydroalkoxylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Qingqing Luo, Zhou Tian, Jie Tang, Jie Wang, Yin Tian, Cheng Peng, Gu Zhan, Bo Han
Summary: The study focuses on the design of bifunctional 4-pyrrolidinopyridines as Lewis base catalysts, which exhibited excellent efficiency and stereoselectivity in asymmetric cycloaddition reactions. The research provides strong support for the construction of chiral spiropyrazolone derivatives.
Article
Chemistry, Physical
Xu Chen, Zhiwei Qiao, Bang Hou, Hong Jiang, Wei Gong, Jinqiao Dong, Hai-Yang Li, Yong Cui, Yan Liu
Summary: Metal-organic frameworks (MOFs) have shown great potential in heterogeneous catalysis, and the enantioselectivities of chiral MOF (CMOF) catalysts can be significantly enhanced by designing metals and ligands, resulting in improved chiral catalytic reactions.
Article
Chemistry, Organic
Skyler D. Mendoza, Michael Rombola, Yujia Tao, Stephan J. Zuend, Roland Goetz, Martin J. McLaughlin, Sarah E. Reisman
Summary: An enantioselective Diels-Alder reaction using yttrium triflate as catalyst has been developed for the synthesis of chiral oxidized cyclohexenes. This method allows the preparation of a key intermediate in the synthesis of commercial herbicide cinmethylin.
Article
Chemistry, Multidisciplinary
Taku Kitanosono, Tomoya Hisada, Yasuhiro Yamashita, Shu Kobayashi
Summary: Metal-bound water molecules have been recognized as a new aspect of soft Lewis acid catalysis. A chiral palladium aqua complex was constructed using a chiral ligand and hydrogen-bond donor, allowing efficient functionalization of carbon-hydrogen bonds of indoles in water. The use of aqueous environments enabled highly enantioselective reactions of sigma-indolylpalladium intermediates, presenting a potentially powerful approach for organometallic transformations under mild conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jia-Bin Pan, Zhi-Chun Yang, Xuan-Ge Zhang, Mao-Lin Li, Qi-Lin Zhou
Summary: Here, we present a method for enantioselective phosphoric acid catalyzed amination of ketenes generated from α-aryl-α-diazoketones. Mechanistic studies elucidated the reaction pathway and explained how the catalyst expedited the transformation and controlled the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Marina Perez-Palau, Nil Sanosa, Pedro Romea, Felix Urpi, Rosa Lopez, Enrique Gomez-Bengoa, Merce Font-Bardia
Summary: A new stereoselective alkylation method has been developed using titanium(IV) enolates of chiral N-acyl oxazolidinones with tert-butyl peresters from Ca-branched aliphatic carboxylic acids. The reaction proceeds through the decarboxylation of peresters and formation of alkyl radicals, resulting in alkylated adducts with excellent diastereoselectivity. Theoretical calculations explain the observed reactivity and outstanding stereocontrol, with the resulting compounds easily converted into ligands for asymmetric and catalytic transformations.
Article
Chemistry, Organic
Lotte Stockhammer, Maximilian Radetzky, Syeda Sadia Khatoon, Matthias Bechmann, Mario Waser
Summary: A two-step protocol for the asymmetric synthesis of novel chiral benzofused ε-lactones starting from O-protected hydroxymethyl-para-quinone methides and activated aryl esters is reported. The use of chiral isothiourea Lewis base catalysts allows the obtaining of a broad variety of differently substituted products with high levels of enantioselectivities.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xiangqing Feng, Wei Meng, Haifeng Du
Summary: Olefins are easily accessible compounds that have dual functions as popular substrates in synthetic chemistry and ligands in organometallic complexes. This study provides a summary of the development of chiral diene ligands and chiral FLP catalysts for asymmetric catalysis. The results show that these ligands and catalysts are highly effective in various asymmetric reactions.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Editorial Material
Chemistry, Multidisciplinary
Bing Fang, Yixuan Li, Fazheng Ren
Summary: In a recent Nature paper, Xu et al. reported the synthesis of chiral Au nanoparticles with the highest g-factor value. These chiral nanoparticles can regulate immune cell maturation, opening up the possibility of using nano scale chirality as an adjuvant for vaccines.
Article
Chemistry, Multidisciplinary
Yusuke Oyamada, Kazuto Inaba, Takahiro Sasamori, Shuichi Nakamura
Summary: This study achieved high enantioselectivity in the reaction of imines by introducing a cyano group as an activating group. The density functional theory (DFT) calculation clarified the stereochemical outcome and importance of the N-cyano group in the reaction.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Naoki Yasukawa, Ami Yamanoue, Tsunayoshi Takehara, Takeyuki Suzuki, Shuichi Nakamura
Summary: The first enantioselective aza-Henry reaction of non-activated cyclic iminoesters, derived from cyclic amino acids, has been developed using a unique cinchona alkaloid sulfonamide/zinc(ii) catalyst. Good yields and enantioselectivities were observed, and the stereochemistry was explained by proposed transition state based on experiments and DFT calculations.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Shuichi Nakamura, Yoichiro Matsuda, Tsunayoshi Takehara, Takeyuki Suzuki
Summary: The first enantioselective Pictet-Spengler reaction of acyclic alpha-ketoesters with tryptamines has been successfully developed. Chiral imidazoline-phosphoric acid catalysts were found to provide excellent yields and enantioselectivity for the reaction. Density functional theory calculations revealed possible transition states, explaining the origin of chiral induction. This process offers an efficient route for the synthesis of tetrahydro-beta-carboline derivatives.
Article
Multidisciplinary Sciences
Satoshi Yamanaka, Yuto Horiuchi, Saya Matsuoka, Kohki Kido, Kohei Nishino, Mayaka Maeno, Norio Shibata, Hidetaka Kosako, Tatsuya Sawasaki
Summary: This article introduces a method based on AirID to identify drug-induced neo-substrates through proximity-dependent biotinylation. The study identifies several new CRBN substrates and demonstrates that this method can serve as a general strategy for studying drug-induced protein-protein interactions in cells.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Hiroto Uno, Koki Kawai, Taichi Araki, Motoo Shiro, Norio Shibata
Summary: Gem-difluoromethylene moieties are attractive in medicinal chemistry due to their ability to mimic other more ubiquitous functional groups. A novel asymmetric method for their construction was developed, allowing easy access to chiral 1,3-dioxanes that contain a tetrasubstituted difluoroalkyl stereogenic center. The gem-difluoro substitution pattern promotes the reaction, and various substrates were suitable for this method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Kazuki Ogura, Itsuki Isozumi, Tsunayoshi Takehara, Takeyuki Suzuki, Shuichi Nakamura
Summary: In this study, the first enantioselective hydrophosphonylation of ketimines with phosphine oxides was developed. The reaction using a bis(imidazoline)-phosphoric acid catalyst resulted in chiral alpha-quaternary aminophosphorous compounds with a primary amino group in excellent yields and enantioselectivities. Transition states were proposed based on experimental results and DFT calculation to explain the stereoselectivity of the reaction.
Article
Chemistry, Applied
Yusuke Oyamada, Shintaro Yamasaki, Mika Tsuzuki, Takumi Kitagawa, Masaru Kondo, Takahiro Sasamori, Shuichi Nakamura
Summary: The catalytic enantioselective allenylation of ketimines derived from isatins is reported. High regio- and enantioselective products were obtained using a bis(imidazoline)-palladium catalyst. The obtained products were further converted into various chiral amines. The stereoselectivity origin was revealed by DFT calculations of the transition state.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Yuka Iizuka, Tatsumi Wada, Kazuki Ogura, Tsunayoshi Takehara, Takeyuki Suzuki, Shuichi Nakamura
Summary: The first enantioselective synthesis of cyclic N,S-ketals having tetrasubstituted chiral center through intramolecular cyclization has been developed. The reaction using a chiral imidazoline-phosphoric acid catalyst shows high enantioselectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Norio Shibata, Dominique Cahard
Summary: From 2000, our two research groups independently and simultaneously designed and developed a novel family of electrophilic fluorinating reagents based on the use of Cinchona alkaloids. The chiral N-fluoro ammonium salts demonstrated the highest efficiency compared to prior art in enantioselective electrophilic fluorination for a wide range of substrates. In this account, we tell our respective stories, how the same idea germinated in our laboratories, the characterization of the chiral reagents, the use in stoichiometric quantity then the development of a catalytic version, the application to the synthesis of chiral fluorinated molecules of pharmaceutical interest, and finally the exploitation of our reagents by other teams and for other applications.
Review
Chemistry, Multidisciplinary
Yuji Sumii, Norio Shibata
Summary: The trifluoromethyl group is a crucial component in drugs and polymers, making the development of trifluoromethylation reactions a significant area of research in organic chemistry. Various methods, including nucleophilic and electrophilic approaches, transition-metal catalysis, photocatalysis, and electrolytic reactions have been developed over the years. Microflow versions of these reactions have shown great potential for industrial applications due to their scalability, safety, and time efficiency. This review discusses the current state of microflow trifluoromethylation, focusing on different trifluoromethylation reagents and techniques such as continuous flow, flow photochemical, microfluidic electrochemical reactions, and large-scale microflow reactions.
Letter
Chemistry, Organic
Elsayed M. Mahmoud, Soichiro Mori, Yuji Sumii, Norio Shibata
Summary: The synthesis of acyl fluorides from carboxylic acids is achieved using Selectfluor mediated by elemental sulfur. A wide range of acyl fluorides can be accessed while avoiding the formation of acid anhydrides. F-19 NMR spectra indicate that the reactive species in this deoxyfluorination reaction are the in situ generated S-8-fluoro-sulfonium cation A and neutral S-8-difluoride A'.
Article
Chemistry, Organic
Shuichi Nakamura, Masato Kibe, Tsunayoshi Takehara, Takeyuki Suzuki
Summary: The first enantioselective reaction of alpha-isocyanoacetonitriles was established using cinchona alkaloid amide-Cu(II) catalysts, resulting in imidazolines with tetrasubstituted stereogenic carbon centers. The reaction exhibited high diastereo- and enantioselectivities, which were explained by control experiments and density functional theory calculations. The conversion of the products into chiral compounds demonstrated the potential application of alpha-isocyanoacetonitriles in asymmetric and organic syntheses.
Article
Multidisciplinary Sciences
Jun Zhou, Zhengyu Zhao, Norio Shibata
Summary: Defluorinative cross-coupling between amines and organic fluorides is achieved via a silylboronate-mediated strategy. This method enables the room-temperature cross-coupling of C-F and N-H bonds, avoiding the high energy barriers associated with thermally induced S(N)2 or S(N)1 amination. The selective activation of the C-F bond of organic fluorides by silylboronate is a significant advantage of this transformation.
NATURE COMMUNICATIONS
(2023)
Editorial Material
Chemistry, Multidisciplinary
Norio Shibata, Dinesh Talwar
Summary: The unique properties and applications of fluorine-containing molecules have had significant impact across different scientific fields, from small to large molecules. This special issue provides a comprehensive overview of the state-of-the-art in fluorine chemistry.
Article
Chemistry, Multidisciplinary
Jun Zhou, Zhengyu Zhao, Bingyao Jiang, Katsuhiro Yamamoto, Yuji Sumii, Norio Shibata
Summary: In this study, an efficient silylboronate-mediated cross-coupling reaction of aryl fluorides with arylalkanes was developed under transition-metal-free, room-temperature conditions. The method showed good adaptability to aryl fluorides with a C(sp(2))-F bond and can be extended to other coupling partners with a C(sp(3))-H bond. It provides a practical and convenient approach to obtain di- and triarylalkanes with tertiary or quaternary carbon centers.
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
