Article
Chemistry, Multidisciplinary
Kazutaka Sanada, Aoi Washio, Hiroki Ishikawa, Yasushi Yoshida, Takashi Mino, Masami Sakamoto
Summary: This article presents a method for chiral symmetry breaking of monoacylated meso diols and demonstrates its effectiveness through experiments and structural analysis. The results show that Viedma ripening can efficiently produce enantiomer crystals, achieving asymmetric expression and amplification of sugar derivatives without an external chemical chiral source. Additionally, the method is successfully applied to asymmetric desymmetrization of acyclic meso-1,2-diols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Hiroki Mandai, Tsubasa Hironaka, Koichi Mitsudo, Seiji Suga
Summary: An efficient enantioselective acylative desymmetrization of cyclic meso-1,3-diols was developed using a chiral DMAP derivative with a 1,1'-binaphthyl unit, showing good to excellent enantioselectivity. The key building block obtained from this transformation can be easily obtained in almost enantiomerically pure form.
Article
Chemistry, Multidisciplinary
Yu Zhanglong, Li Zhongliang, Yang Changjiang, Gu Qiangshuai, Liu Xinyuan
Summary: This review summarizes the research progress in copper-catalyzed enantioselective desymmetrization of diols, and provides a brief perspective on its application prospects in medicinal chemistry, total synthesis, and materials science.
ACTA CHIMICA SINICA
(2023)
Article
Chemistry, Multidisciplinary
Sourav Dutta, Arka Porey, Joyram Guin
Summary: Here, we present an efficient strategy for the enantioselective synthesis of oxindoles with a C3-quaternary stereocenter using N-heterocyclic carbene (NHC) catalyzed desymmetrization of diols. The process involves the catalytic asymmetric transfer acylation of primary alcohols using readily available aldehydes. This reaction provides easy access to diverse C3-quaternary oxindoles with excellent enantioselectivity. The synthetic potential of the process is demonstrated through the preparation of key intermediates for (-)-esermethole and (-)-physostigmine.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Kotaro Ikeda, Shingo Harada, Yoshinori Hashimoto, Haruka Homma, Masato Kono, Nadine Zumbraegel, Harald Groeger, Tetsuhiro Nemoto
Summary: In this study, an optically active isoquinuclidine with four chiral carbon centers was obtained using enzymatic desymmetrization. Additionally, a pentacyclic intermediate for catharanthine was synthesized in an enantioenriched form through late-stage construction of the common Iboga scaffold.
Article
Biotechnology & Applied Microbiology
Tatiana Ziemniczak Pereira de Figueiredo, Fernando Augusto Pedersen Voll, Nadia Krieger, David Alexander Mitchell
Summary: The lipase-catalyzed kinetic resolution of chiral diols or the desymmetrization of achiral meso-diols involves two alternative routes, each consisting of two steps. The selectivities of the lipase for different nucleophiles competing to attack the acyl-enzyme intermediate during these reactions are critical for the success of the resolution process and for the mathematical models describing these processes. Current methods for estimating these selectivities are not accurate enough. In this study, a new approach based on a model using selectivities as the only parameters is developed to determine selectivities in lipase-catalyzed desymmetrization or resolution reactions with diols. The advantages of this method over previously proposed methods are demonstrated using literature data from three case studies of increasing complexity.
BIOCHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Organic
Sai-Ya Lian, Ning Li, Yin Tian, Cheng Peng, Ming-Sheng Xie, Hai-Ming Guo
Summary: This study reports a desymmetrization reaction of meso-vic-diols with a reversal of enantioselectivity catalyzed by chiral pyridine-N-oxides with l-proline as a single source of chirality. The reaction achieved a complete and controlled switch in stereoselectivity, and chiral six-membered carbocyclic uracil nucleosides were generated with excellent enantioselectivities. Through control experiments and density functional theory calculations, it was confirmed that the reaction proceeded in a bifunctional activated manner, and the distance-directed switching of enantioselectivity played a vital role.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jung Tae Han, Hui Zhou, Benjamin List
Summary: We describe a Brønsted acid-catalyzed enantioselective silylation of biaryl diols using an allylsilane as a source of silicon. This method allows for easy access to enantioenriched biaryl silyl ethers with axial stereogenicity. A control experiment confirms a mechanism involving desymmetrization followed by kinetic resolution.
Article
Chemistry, Physical
Irene Sanchez-Sordo, Andrea Chaves-Pouso, Jaime Mateos-Gil, Eva Rivera-Chao, Martin Fananas-Mastral
Summary: In this study, a new copper-catalyzed coupling reaction is reported for the enantioselective desymmetrization of chiral cycloalkenes. The method allows for the synthesis of chiral products with high regio-, diastereo-, and enantioselectivity, which can serve as versatile building blocks for the synthesis of various optically active cyclic compounds.
Article
Chemistry, Organic
Stefan Malatinec, Eva Bednarova, Hiroki Tanaka, Martin Kotora
Summary: This study presents a catalytic and highly enantioselective ring-opening reaction of epoxides, utilizing newly designed chiral bipyridine ligands. A Sc-complex with a newly developed bipyridine ligand demonstrated high reactivity and stereocontrol in the desymmetrization of meso-epoxides with various alcohols, achieving enantioenriched 1,2-alkoxyalcohols with high e.r. values. Additionally, attempted ring-opening of meso-epoxides with anilines showed lower enantioselectivity, dependent on the electronic effect of substituents on the aromatic ring.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Tian-Yuan Zhao, Ke Li, Liang-Liang Yang, Shou-Fei Zhu, Qi-Lin Zhou
Summary: The highly enantioselective and diastereoselective nickel-catalyzed desymmetrizing cyclization of 1,6-dienes using chiral spiro phosphoramidite ligands provides a new atom- and step-economic approach to chiral spiro lactones and analogues bearing a quaternary stereo-center, which holds significant synthetic application value.
Article
Chemistry, Multidisciplinary
Min Zhu, Hua-Jie Jiang, Illia Sharanov, Elisabeth Irran, Martin Oestreich
Summary: A desymmetrizing silylation of aromatic diols is achieved by using List's counteranion directed silylation technique for asymmetric silyl ether formation of phenol derivatives. The enantioselective discrimination of achiral 1,1'-biaryl-2,6-diols is enabled by a silylium-ion-like silicon electrophile generated from an allylic silane paired with an imidodiphosphorimidate (IDPi). The enantioselectivity of the desymmetrization is further improved by a downstream kinetic resolution, converting the monosilylated minor enantiomer into the corresponding bissilylated diol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yu-Fei Ao, Hui-Juan Hu, Cheng-Xin Zhao, Peng Chen, Tingting Huang, Hui Chen, Qi-Qiang Wang, De-Xian Wang, Mei-Xiang Wang
Summary: This study demonstrates efficient biocatalytic desymmetrization of meso O-heterocyclic dicarboxamides for synthesizing both antipodes of functionalized cyclic motifs, with yields up to 99.5% ee. The engineered biocatalyst shows wide substrate promiscuity, high efficiency, and excellent enantioselectivity.
Article
Chemistry, Multidisciplinary
Wenpeng Ma, Li-Chuan Liu, Kun An, Tao He, Wei He
Summary: A Rh-catalyzed desymmetrization of dihydrosilanes under simple and mild conditions provides easy access to a range of chiral monohydrosilanes with good yields and excellent enantioselectivities (up to >99% ee). These monohydrosilanes serve as a useful platform to access stereogenic silicon compounds and probe silicon stereochemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Qing-Shan Kong, Xing-Long Li, Hong-Bo Shen, Hua-Jian Xu, Yao Fu
Summary: This study presents an eco-friendly and efficient heterogeneous sodium-doped porous sodium manganese oxide catalyst for the oxidative cleavage of furanic 1,2-diols into medium-chain furanic aldehyde compounds. Various high value-added chemicals were synthesized using this catalytic approach, demonstrating its broad applicability and high selectivity.
GREEN ENERGY & ENVIRONMENT
(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, Multidisciplinary
Yuta Sato, Tsuyoshi Matsuzaki, Tsunayoshi Takehara, Makoto Sako, Takeyuki Suzuki, Mitsuhiro Arisawa
Summary: Multitasking single-catalyst systems are crucial for eco-compatible chemistry, and we have developed a rhodium-catalyzed system that can convert 1-(allyloxy)-2-(cyclopropylmethyl)benzene derivatives to 2-ethyl-3-isopropylbenzofurans via double isomerization/cycloisomerization/aromatization.
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
Chemistry, Organic
Rui Jiang, Ismiyarto, Tsukasa Abe, Da-Yang Zhou, Kaori Asano, Takayoshi Suzuki, Hiroaki Sasai, Takeyuki Suzuki
Summary: In the context of asymmetric synthesis, epimerization has been a challenge. In this study, the epimerization of gamma-butyrolactone was used to synthesize enterolactones with various biological activities. The selective alpha or beta-epimerization allowed the synthesis of both enantiomers of enterolactone. The mechanism of the epimerization was elucidated through theoretical and kinetic studies.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Nanoscience & Nanotechnology
Honami Iguchi, Mitsuru Inada, Shunsuke Aratani, Moegi Nomura, Takeyuki Suzuki, Yuan Jing, Takashi Toyao, Zen Maeno, Ken-ichi Shimizu, Yasushi Obora
Summary: This study reports the use of niobium nanoparticles as quantum dot phosphors. The nanoparticles were synthesized by liquid-phase reduction, and their intense fluorescence was observed. Monodisperse particles with a diameter of less than 10 nm were prepared by adding trimethylsilyl chloride. X-ray photoelectron microscopy and X-ray absorption spectroscopy measurements confirmed the reduction of the valence of niobium nanoparticles compared to the precursor. A device fabricated from these nanoparticles emitted light in the visible-light region.
ACS APPLIED NANO MATERIALS
(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, Inorganic & Nuclear
Ray Miyazaki, Kenji Iida, Shohei Ohno, Tsuyoshi Matsuzaki, Takeyuki Suzuki, Mitsuhiro Arisawa, Jun-ya Hasegawa
Summary: 2,3-disubstituted benzofurans with potential for pharmaceutical applications are effectively synthesized by Ni complexes via intramolecular C-O bond activation. The reaction pathway of the catalytic cycle has been studied using density functional theory (DFT) calculations. It was found that the rate-determining step is the reductive elimination of the product. A key finding is that coordination to an alkynyl group of another substrate occurs simultaneously with elimination, enhancing the thermodynamic stability of the product and determining the reaction pathway of the catalytic cycle. The reductive elimination assisted by solvent molecules or free ligand results in an endergonic reaction. This result can be considered as a self-cocatalytic effect of the substrate and adds a new perspective to the design of catalytic reaction systems with effective catalytic cycles.
Article
Chemistry, Organic
Rui Jiang, Da-Yang Zhou, Kaori Asano, Takayoshi Suzuki, Takeyuki Suzuki
Summary: The catalytic asymmetric synthesis of (-)-arctigenin was achieved through the transformation of the central optically pure lactone intermediate and the introduction of aryl units. Various coupling protocols were studied for the incorporation of the first aryl unit, while a diastereoselective Rh-catalyzed conjugate addition was utilized for the addition of the second aryl unit.
Article
Chemistry, Medicinal
Satoru Hirabayashi, Yuko Tsuyuguchi, Yue Li, Noriko Ohta, Yusuke Yoshikawa, Bangzhong Lin, Megumi Fumimoto, Kazuto Nunomura, Takeyuki Suzuki, Junichi Haruta, Keisuke Nimura, Mitsuhiro Arisawa
Summary: We designed and synthesized novel derivatives of spliceostatin A with modified 4-acetoxypentanamide moiety through reduction (7), isomerization (8), or substitution with methyl at the α-position (9). The biological evaluation and docking analysis of each derivative indicate that the geometric configuration of the 4-acetoxypentenamide moiety of spliceostatin A is crucial for its biological activity.
BIOORGANIC & MEDICINAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Organic
Yuta Chikashige, Tsunayoshi Takehara, Tsuyoshi Matsuzaki, Takeyuki Suzuki, Kenichi Murai, Mitsuhiro Arisawa, Makoto Sako
Summary: A novel chiral borinic acid (CBA) with a binaphthyl skeleton was successfully designed and synthesized. The synthesis of CBA was achieved starting from optically pure 1,1'-bi-2-naphthol and resulted in a 72% yield in four steps. The asymmetric catalytic activity of CBA was investigated in the desymmetrization of meso-1,2-diol.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shohei Yoshioka, Masaharu Takatsuki, Tsunayoshi Takehara, Takeyuki Suzuki, Mitsuhiro Arisawa
Summary: Sulfonylindoles were synthesized via migratory cycloisomerization using an allene N-tosyl-o-allenylaniline. 3-tosyl indoles or 4-tosyl indoles were selectively produced using a Pd catalyst or a Au catalyst, respectively.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Kazuki Tateishi, Tomoya Tada, Taichi Sotani, Takeyuki Suzuki, Hiromitsu Sogawa, Fumio Sanda
Summary: This paper reports on photoluminescent supramolecular gels derived from phenylenediamine hydrochlorides. Compound 1L underwent gelation in THF and CHCl3, but not in alcohols, DMSO, and DMF. The gel exhibited different fluorescence emission compared to the sol state. Molecular dynamics simulations and dynamic light scattering measurements supported the gelation of 1L in THF and CHCl3.
Article
Chemistry, Inorganic & Nuclear
Ken Motohara, Kazuhiro Kado, Taichi Sotani, Dayang Zhou, Takeyuki Suzuki, Hiromitsu Sogawa, Fumio Sanda
Summary: A novel conjugated platinacycle was synthesized by the dehydrochlorination coupling reaction of a bipyridine dichloroplatinum(ii) complex and a 3,6-diethynylcarbazol derivative. The structure of the platinacycle was confirmed by various spectroscopic techniques and DFT calculations. The platinacycle displayed unique photoelectric properties including ligand-ligand charge transfer absorption and birefringence in DMF due to molecular alignment.
DALTON TRANSACTIONS
(2023)
Article
Polymer Science
Masanobu Muraoka, Masahide Goto, Masaki Minami, Dayang Zhou, Takeyuki Suzuki, Tatsuo Yajima, Jun'ichi Hayashi, Hiromitsu Sogawa, Fumio Sanda
Summary: Benzoxazine is a promising thermosetting resin with catalyst-free curing, high thermal stability, and low volume shrinkage upon curing. The difunctional benzoxazine showed a higher curing temperature and higher weight maintenance at high temperatures compared to the monofunctional and trifunctional benzoxazines. This stability is likely due to the more regulated molecular arrangement of the difunctional benzoxazine. Additionally, the cured resins showed different CO2 adsorption capacities, with poly(2) having the highest adsorption.
Article
Chemistry, Organic
Masayuki Kirihara, Riho Nakamura, Kana Nakakura, Kazuki Tujimoto, Mohamed S. H. Salem, Takeyuki Suzuki, Shinobu Takizawa
Summary: A diethylaminosulfur trifluoride (DAST)-mediated ring-opening reaction of cyclopropyl silyl ethers in nitriles has been successfully achieved, leading to the formation of allylic amides. Time course studies using ReactIR and O-isotopic labeling mechanistic studies have revealed the mechanism of this reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
