Article
Chemistry, Multidisciplinary
Hanyang Bao, Yunrong Chen, Xiaoyu Yang
Summary: In this study, a highly efficient catalytic asymmetric synthesis of diaryl ether atropisomers was reported via an organocatalyzed enantioselective desymmetrization protocol. The chiral phosphoric acid-catalyzed asymmetric electrophilic aromatic aminations of symmetrical substrates provided a series of diaryl ether atropisomers with excellent yields and enantioselectivities. The utilization of the 1,2-benzenediamine moiety in the products allowed for the facile construction of heterocycles, leading to a wide range of structurally diverse and novel azaarene-containing diaryl ether atropisomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Guang-Jian Mei, Jonathan J. Wong, Wenrui Zheng, Anjanay A. Nangia, K. N. Houk, Yixin Lu
Summary: The first catalytic asymmetric synthesis of N-N axially chiral compounds has been achieved, adding a new dimension to axially chiral molecules and atropisomerism. DFT calculations have been used to understand enantioselectivity and guide the design of similar molecules. Research on N-N axial atropisomerism holds promise for new discoveries in medicinal chemistry and asymmetric catalysis.
Article
Multidisciplinary Sciences
Fengyuan Guo, Siqiang Fang, Jiajia He, Zhishan Su, Tianli Wang
Summary: This article discusses an organocatalytic asymmetric nucleophilic aromatic substitution reaction, offering a pathway to axial styrene scaffolds via a dynamic kinetic resolution process using a hemiacetal intermediate.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
John R. J. Maynard, Peter Gallagher, David Lozano, Patrick Butler, Stephen M. Goldup
Summary: Chirality typically arises in molecules, but can also be created through interthreading molecules to form mechanical bonds. In this study, the symmetry properties of these molecules were re-examined, leading to the discovery of a straightforward method to access enantiopure mechanically axially chiral molecules.
Article
Chemistry, Multidisciplinary
Qian-Yi Zhou, Xin Li
Summary: In this study, a unique family of axially chiral enamides was synthesized catalytically with good yields and excellent enantioselectivities under mild conditions. These new compounds possess a flexible structure and a high degree of rotational freedom, which introduces challenges for enantiocontrol. A proposed mechanism model suggests that both the steric difference of the ortho substituents and the pi-pi stacking interaction may contribute to the stereo-control.
CHEMICAL COMMUNICATIONS
(2022)
Review
Multidisciplinary Sciences
Ana Maria Faisca Phillips, Armando J. L. Pombeiro
Summary: Atropisomers, which are stereoisomers hindered in their rotation due to steric interactions or electrostatics, exhibit unique characteristics and can be found in various applications. The synthesis of atropisomers containing C-N and N-N axes of chirality has become a hot topic in research, focusing on sustainable synthesis using achiral materials and organocatalysts under mild conditions. This review provides an overview of recent achievements in this field.
Article
Chemistry, Organic
Alemayehu Gashaw Woldegiorgis, Haorui Gu, Xufeng Lin
Summary: The organocatalytic asymmetric reactions of C2-unsubstituted racemic naphthyl-indoles with orthoalkynylnaphthols were used to synthesize axially chiral styrenes connected to an axially chiral naphthyl-indole unit. By employing chiral phosphoric acid as the catalyst, these axially chiral styrenes were obtained in good yields (up to 96%) and excellent stereoselectivity (up to >99.9% ee, >20:1 dr, and >99:1 E/Z) under mild conditions. Furthermore, further synthetic transformations were achieved with high yields and excellent stereocontrol.
Article
Multidisciplinary Sciences
Jie Han, Siyuan Liu, Huanan Wang, Jie Wang, Hui Qian, Zhiming Li, Shengming Ma, Junliang Zhang
Summary: The 13-H elimination is a crucial step in the carbon-palladium bond quenching for the Heck reaction and has been a challenge to control enantioselectivity. Here, we developed a concise and efficient method to construct chiral allenes from fully substituted enol triflates through enantioselective 13-H elimination of alkenyl palladium species under mild conditions. The identified Xu-Phos catalysts play a crucial role in chemoselectivity and enantioselectivity. Multiple linear regression analysis shows the significance of steric effect on enantioselectivity. DFT calculations propose an intramolecular base-assisted deprotonation mechanism for this progress, and energy decomposition analysis suggests that the difference in electrostatic energy of the transition states dominates the stereoselectivity.
Article
Chemistry, Organic
Shinya Tajima, Atsuya Muranaka, Masaya Naito, Noriho Taniguch, Mei Harada, Shinobu Miyagawa, Masahiro Ueda, Hikaru Takaya, Nagao Kobayashi, Masanobu Uchiyama, Yuji Tokunaga
Summary: In this study, a [2]rotaxane with both mechanically planar chiral and axially chiral properties was synthesized, consisting of a symmetrical biscrown ether with a biphenyl moiety as the macrocyclic component and a symmetrical bis-ammonium salt as the dumbbell-shaped component.
Article
Chemistry, Organic
Ari Hakgor, Sule Erol Gunal
Summary: Axially chiral 2-thioxo-3-(o-aryl)-quinazolin-4-ones and 2-(benzylthio)-3-(o-aryl)-quinazolin-4-ones were synthesized, and the rotational barriers about the N-3-C-aryl bond were determined. The rotational barriers were found to increase linearly with the size of ortho substituents, and compounds bearing an ortho-fluoro group had high enough rotational barriers for enantiomer isolation.
Article
Multidisciplinary Sciences
Jia-Lei Yan, Rakesh Maiti, Shi-Chao Ren, Weiyi Tian, Tingting Li, Jun Xu, Bivas Mondal, Zhichao Jin, Yonggui Robin Chi
Summary: In this study, a chiral solution utilizing N-heterocyclic carbene (NHC) catalyst was developed for the preparation of axially chiral styrenes with high enantioselectivity and excellent yields. The sulfone and carboxylic ester moieties in the styrenes are common functional groups in bioactive molecules and asymmetric catalysis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Peng Zhang, Jia Feng, Ren-rong Uu
Summary: Benzimidazole atropisomers with a C-N axis are privileged structural frameworks in pharmaceutical and natural products, and their asymmetric synthesis has attracted increasing attention. This paper briefly discusses recent advances in the asymmetric synthesis of benzimidazole atropisomers with a C-N axis, focusing on the recently developed palladium-catalyzed intramolecular Buchwald-Hartwig amination strategy.
Article
Chemistry, Physical
Jintong Song, Yanying Wang, Lang Qu, Lizhi Fang, Xiangge Zhou, Zong-Xiang Xu, Cheng Yang, Peng Wu, Haifeng Xiang
Summary: By designing and preparing highly pure bicarbazole materials, high-performance ultralong room-temperature phosphorescence (RTP) has been achieved. The material also exhibits photoactivated delayed fluorescence and RTP properties, making it a promising tool for rejuvenating carbazole-based RTP.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Organic
Prashant Kumar, Rajendra P. Shirke, Sonu Yadav, S. S. Ramasastry
Summary: The study introduces a novel method for the synthesis of axially chiral (Z)-diarylmethylidene indanones (DAIs) and demonstrates a general and efficient protocol for both racemic and atropselective synthesis. An unconventional intramolecular Morita-Baylis-Hillman reaction is used for the Z-selective synthesis of beta-keto enol triflates.
Article
Chemistry, Organic
Ziyue Liu, Ben Gao, Konstantin Chernichenko, He Yang, Sebastien Lemaire, Wenjun Tang
Summary: An enantioselective palladium-catalyzed C-H arylation of functionalized pyrazoles/triazoles/imidazoles has been developed, yielding axially chiral ortho-nitro/formyl-substituted heterobiaryls with high enantioselectivity and good yields.
Article
Chemistry, Multidisciplinary
Yumiko Iwasaki, Ryuichi Morisawa, Satoshi Yokojima, Hiroshi Hasegawa, Christian Roussel, Nicolas Vanthuyne, Elsa Caytan, Osamu Kitagawa
CHEMISTRY-A EUROPEAN JOURNAL
(2018)
Article
Chemistry, Medicinal
Wenzhong Zhang, Romuald Eto Ekomo, Christian Roussel, Hiroki Moriwaki, Hidenori Abe, Jianlin Han, Vadim A. Soloshonok
Article
Chemistry, Organic
Vesna Risso, Daniel Farran, Guilhem Javierre, Jean-Valere Naubron, Michel Giorgi, Patrick Piras, Marion Jean, Nicolas Vanthuyne, Roberta Fruttero, Dominique Lorcy, Christian Roussel
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Medicinal
Jianlin Han, Marion Jean, Christian Roussel, Hiroki Moriwaki, Vadim A. Soloshonok
Article
Chemistry, Medicinal
Haibo Mei, Marion Jean, Muriel Albalat, Nicolas Vanthuyne, Christian Roussel, Hiroki Moriwaki, Zizhen Yin, Jianlin Han, Vadim A. Soloshonok
Article
Chemistry, Organic
Asumi Iida, Mizuki Matsuoka, Hiroshi Hasegawa, Nicolas Vanthuyne, Daniel Farran, Christian Roussel, Osamu Kitagawa
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Gaku Furukawa, Takeshi Shirai, Yuki Homma, Elsa Caytan, Nicolas Vanthuyne, Daniel Farran, Christian Roussel, Osamu Kitagawa
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
David Nunez Alonso, Marta Perez-Torralba, Rosa M. Claramunt, M. Carmen Torralba, Patricia Delgado-Martinez, Ibon Alkorta, Jose Elguero, Christian Roussel
Article
Chemistry, Organic
Ophelie Quinonero, Clement Lemaitre, Marion Jean, Nicolas Vanthuyne, Christian Roussel, Damien Bonne, Thierry Constantieux, Cyril Bressy, Xavier Bugaut, Jean Rodriguez
Summary: This reinvestigation focused on a chiral phosphoric acid-catalyzed synthesis of polyhydroquinolines reported in 2009, revealing a lack of enantioselectivity with the use of chiral enantiopure phosphoric acid catalyst as opposed to the original report. The new Enantioselectivity results were confirmed through baseline separation of enantiomers using HPLC analyses on chiral stationary phase with UV and chiroptical detection.
Article
Chemistry, Organic
Kazuya Saito, Shota Miwa, Asumi Iida, Yuuki Fujimoto, Elsa Caytan, Christian Roussel, Osamu Kitagawa
Summary: In this study, racemic and optically active 3-(2-deuteriophenyl)-2-(1-phenylpropan-2-yl) quinazoline-4-thiones were successfully prepared. Nuclear magnetic resonance spectra clearly demonstrated that they exist as a 1:1 mixture of diastereomers due to isotopic atropisomerism and chiral carbon.
Article
Chemistry, Organic
Ibon Alkorta, Rosa M. Claramunt, Jose Elguero, Enrique Gutierrez-Puebla, M. Angeles Monge, Felipe Reviriego, Christian Roussel
Summary: The reaction between NH-indazoles and formaldehyde in aqueous hydrochloric acid was experimentally studied using solution and solid-state nuclear magnetic resonance and crystallography. The mechanism of N1-CH2OH derivative formation was determined. For the first time, 2-substituted derivatives were characterized using multinuclear NMR. Theoretical calculations supported the experimental observations. Additionally, the X-ray structures of four new (1H-indazol-1-yl)methanol derivatives were reported.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Daiki Homma, Shuhei Taketani, Takeshi Shirai, Elsa Caytan, Christian Roussel, Jose Elguero, Ibon Alkorta, Osamu Kitagawa
Summary: In this study, N-methyl-2-methoxymethylanilines bearing various 5-substituted-pyrimidin-2-yl groups were synthesized and their rotational behaviors were investigated. The results revealed that the rotational barriers around the N-Ar bonds increase proportionally to the electron-withdrawing ability of the substituent X at the S position.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Daniel Farran, Nicolas Vanthuyne, Giulia Bossa, Vincent Belot, Muriel Albalat, Marion Jean, Christian Roussel
Summary: A study on compounds based on N-arylthiazoline scaffold was conducted, synthesizing 22 structures with a N-C-aryl chiral axis and determining their rotational barriers, showing significant influence of flanking substituents on stability.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Dionisia Sanz, Rosa M. Claramunt, Christian Roussel, Ibon Alkorta, Jose Elguero
INDIAN JOURNAL OF HETEROCYCLIC CHEMISTRY
(2018)
Article
Chemistry, Medicinal
Nidal Saleh, Radovan Bast, Nicolas Vanthuyne, Christian Roussel, Trond Saue, Benoit Darquie, Jeanne Crassous
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)
