Article
Chemistry, Multidisciplinary
Liam A. McLean, Matthew W. Ashford, James W. B. Fyfe, Alexandra M. Z. Slawin, Andrew G. Leach, Allan J. B. Watson
Summary: We have reported a method for synthesizing chiral vicinal chloroamines through asymmetric protonation using chiral Bronsted acids. The process is highly selective and the origins of asymmetry and the effects of catalyst substitutions have been clarified by DFT calculations. Additionally, we have demonstrated the utility of this method in synthesizing a wide range of heterocycle-substituted aziridines and vicinal diamines.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jin Jiaping, Alemayehu Gashaw Woldegiorgis, Xufeng Lin
Summary: Here, we report an enantioselective protocol for the chiral phosphoric acid-catalyzed addition of 3-arylisoxazol-5-amines to highly reactive 3-methide-3H-pyrroles. This protocol provides a diverse range of heterotriarylmethanes bearing an amino acid moiety in good yields (up to 97%) and high enantioselectivities (up to 93% ee) under mild conditions. The utilization of a chiral spirocyclic phosphoric acid is crucial in converting the initial 1H-pyrrol-3-yl carbinols into reactive 3-methide-3H-pyrroles and achieving the desired enantioselective transformation.
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, Physical
Jiayan Li, Changgui Zhao
Summary: Planar-chiral cyclophanes have unique properties and are important for drug discovery. However, the catalytic asymmetric synthesis of planar-chiral cyclophanes has been a challenge. We report a new reaction method for the high-yield, high-eselectivity synthesis of chiral planar cyclophanes. Through studying the reaction mechanism and enantioselectivity, we gain a deeper understanding of the process.
Article
Chemistry, Multidisciplinary
Thomas Varlet, Mateja Matisic, Elsa Van Elslande, Luc Neuville, Vincent Gandon, Geraldine Masson
Summary: A diastereodivergent and enantioselective synthesis of chiral spirocyclohexyl-indolenines with four contiguous stereo-genic centers was achieved through a chiral phosphoric acid-catalyzed cycloaddition. By carefully choosing reaction conditions, modular access to two different diastereoisomers with high enantioselectivities was obtained. The functional group manipulation of these compounds provides an efficient access to enantioenriched spirocyclohexyl-indolines and -oxindoles.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Kai Matsui, Kohei Toh, Manabu Hatano, Kazuaki Ishihara
Summary: A multiselective Diels-Alder reaction involving alpha-arylacroleins and cyclopentadiene has been developed using BBr3-assisted chiral BINOL-derived phosphoric acid catalysts. The chiral cavity of the in situ-formed acid-base cooperative catalysts plays a key role in controlling the exo- and enantioselectivity, particularly by suppressing the competitive hetero Diels-Alder reaction effectively.
Review
Chemistry, Multidisciplinary
Pu-Fan Qian, Tao Zhou, Bing-Feng Shi
Summary: This feature article provides a comprehensive understanding of recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals, integrating scattered work with different catalytic systems.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Pinke Yu, Danyi Chen, Yiwen Liu, Congcong Yin, Qixing Liu, Haifeng Zhou
Summary: An asymmetric transfer hydrogenation of 2-oxazolones using a chiral diamine ruthenium catalyst, potassium formate as a hydrogen source, potassium carbonate as an additive in 2,2,2-trifluoroethanol has been described. The reaction yielded a series of chiral 2-oxazolidinones with 29%-95% yields and 86%->99% ee's. Gram-scale synthesis and downstream derivatizations of chiral 2-oxazolidinone demonstrate the practicality of this method.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Chenxiao Qian, Meiwen Liu, Jianwei Sun, Pengfei Li
Summary: Propargylic alcohols are useful substrates in asymmetric reactions, and chiral phosphoric acid catalysis enables the synthesis of chiral tetrasubstituted allenes. This study expands the scope of propargylic alcohols and proposes a possible covalent activation mode.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Jin-fang Chen, Jin-yi Shi, Cong-cong Yin, Xin Cui, Guang-xun Li, Zhuo Tang, Jin-zhong Zhao
Summary: In this study, N-aryl benzimidazoline produced in situ was utilized as a H-2 donor, and through CPA-catalyzed enantioselective transfer hydrogenation, it was converted to C-N axially chiral N-aryl benzimidazole.
NEW JOURNAL OF CHEMISTRY
(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, Physical
Santosh K. Pagire, Naoya Kumagai, Masakatsu Shibasaki
Summary: The catalytic asymmetric cyclopropanation of alpha,beta-unsaturated amides with stabilized sulfur ylides has been successfully achieved with high yields and selectivities, providing a new synthetic route for cyclopropanes.
Article
Chemistry, Multidisciplinary
En Li, Qian Wang, Yuxing Cai, Jiean Chen, Yong Huang
Summary: This study highlights the enantioselective phospha-Michael addition reaction leading to alpha-chiral phosphine sulfide, with an essential role of an independent hydrogen-bonding co-catalyst for high enantioselectivity. Divergent derivatizations under mild conditions for generic phosphine and phosphine oxide compounds further emphasize the bridging role of phosphine sulfide.
CELL REPORTS PHYSICAL SCIENCE
(2021)
Article
Chemistry, Organic
Tao Zhou, Ling-Jie Fan, Zi-Jia Chen, Meng-Xue Jiang, Pu-Fan Qian, Xinquan Hu, Kun Zhang, Bing-Feng Shi
Summary: In this study, we describe the preparation of various structurally diverse P-stereogenic phosphinamides through Pd(II)-catalyzed enantioselective C-H alkynylation using cheap commercially available l-pyroglutamic acid as a chiral ligand. The reactions showed good yields and high enantioselectivities via desymmetrization and kinetic resolution. The presence of a tailor-made congested directing group, N-ethyl-N-(3-methylpyridin-2-yl)amino, was crucial for the reactivity.
Review
Chemistry, Multidisciplinary
Zhi-Yong Han, Liu-Zhu Gong
Summary: Asymmetric Bronsted acid catalysis is a powerful concept for asymmetric synthesis. Chiral bisphosphoric acids have received much attention in the last two decades due to their unique catalytic properties attributed to intramolecular hydrogen bonding interactions. Many structurally unique and effective bisphosphoric acids have been synthesized, exhibiting superior selectivity in a broad range of asymmetric transformations. This review provides an overview of chiral bisphosphoric acid catalysts and their applications in catalyzing asymmetric transformations.
Article
Chemistry, Multidisciplinary
Takuya Hashimoto, Kohei Takino, Kazuki Hato, Keiji Maruoka
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2016)
Article
Chemistry, Multidisciplinary
Yu Kawamata, Takuya Hashimoto, Keiji Maruoka
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2016)
Article
Chemistry, Multidisciplinary
Takuya Hashimoto, Yuto Shimazaki, Yamato Omatsu, Keiji Maruoka
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2018)
Article
Chemistry, Multidisciplinary
Martin Pawliczek, Yuto Shimazaki, Hidenori Kimura, Kevin M. Oberg, Saman Zakpur, Takuya Hashimoto, Keiji Maruoka
CHEMICAL COMMUNICATIONS
(2018)
Article
Chemistry, Multidisciplinary
Martin Pawliczek, Takuya Hashimoto, Keiji Maruoka
Article
Biochemical Research Methods
Neil J. Stewart, Hiroyuki Kumeta, Mitsushi Tomohiro, Takuya Hashimoto, Noriyuki Hatae, Shingo Matsumoto
JOURNAL OF MAGNETIC RESONANCE
(2018)
Article
Multidisciplinary Sciences
Kumiko Yamamoto, Jiakun Li, Jeffrey A. O. Garber, Julian D. Rolfes, Gregory B. Boursalian, Jannik C. Borghs, Christophe Genicot, Jerome Jacq, Maurice van Gastel, Frank Neese, Tobias Ritter
Article
Chemistry, Organic
Yuta Otsuka, Yuto Shimazaki, Hitoshi Nagaoka, Keiji Maruoka, Takuya Hashimoto
Article
Chemistry, Multidisciplinary
Chisato Wata, Takuya Hashimoto
Summary: Metal-free, catalytic enantioselective intermolecular oxyamination of alkenes is achieved using organoiodine(I/III) chemistry. The reaction shows high enantioselectivity and electronically controlled regioselectivity with aryl- and alkyl-substituted alkenes. Key to the success is the discovery of N-(fluorosulfonyl) carbamate as a bifunctional N,O-nucleophile, allowing easy deprotection to yield free amino alcohols without loss of enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Neil J. Stewart, Hitomi Nakano, Shuto Sugai, Mitsushi Tomohiro, Yuki Kase, Yoshiki Uchio, Toru Yamaguchi, Yujirou Matsuo, Tatsuya Naganuma, Norihiko Takeda, Ikuya Nishimura, Hiroshi Hirata, Takuya Hashimoto, Shingo Matsumoto
Summary: A cost-effective synthetic pathway for high-yield hydrogenation precursor was developed, with the trans-selectivity of the hydrogenation reaction elucidated using density functional theory simulations. The study successfully demonstrated the generation of hyperpolarized [1-C-13]fumarate through a simple PHIP set-up, allowing for ex vivo detection in murine liver tissue homogenates and in vivo MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis.
Article
Chemistry, Organic
Chisato Wata, Takuya Hashimoto
Summary: The enantioselective intramolecular oxyaminations were achieved by utilizing benzyl N-(fluorosulfonyl)carbamate as the exogenous nitrogen source in Organoiodine-catalyzed reactions. This method allows the formation of enantioenriched lactones and oxazolines from gamma,delta- and delta,epsilon-unsaturated esters and N-allyl amides.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Yuto Shimazaki, Chisato Wata, Takuya Hashimoto, Keiji Maruoka
Summary: The development of an enantioselective oxidative para-dearomatization of sulfonanilides using an indanol-based chiral organoiodine catalyst in water was reported. This reaction efficiently proceeds with N-mesyl-protected anilines as substrates, yielding functionalized p-quinol imines in good yields and moderate to high enantioselectivities.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yuno Oe, Ryuhei Yoshida, Airi Tanaka, Akiya Adachi, Yuichiro Ishibashi, Takashi Okazoe, Kohsuke Aikawa, Takuya Hashimoto
Summary: This study reports the development of a novel N-fluorinated imide (NFC) as a synthetic handle for the one-step derivatization to amines, sulfonamides, and sulfamides. It also demonstrates the superior reactivity of NFC in copper-catalyzed imidation of benzene derivatives and imidocyanation of aliphatic alkenes, overcoming the limitations of NFSI-mediated reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Hiroto Kimura, Kohsuke Aikawa, Takuya Hashimoto
Summary: CuAAC and SuFEx reactions are two important methods for connecting molecules in click chemistry. This study presents a copper-catalyzed aminoazidation reaction using NFC, which attaches both an azide and a fluorosulfonyl group to an alkene in one step. The derivatization of the product through consecutive CuAAC and SuFEx reactions allows rapid diversification of molecular structure.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Alexander Arlt, Hideaki Toyama, Koji Takada, Takuya Hashimoto, Keiji Maruoka
CHEMICAL COMMUNICATIONS
(2017)
