Article
Chemistry, Physical
Kohei Nishi, Hayato Tsurugi, Kazushi Mashima
Summary: Chromium(III) trichloride combined with aryl/alkyl Grignard reagents showed high catalytic activity for the synthesis of syn-2-aryl/alkyl-1,2-dihydronaphthalen-1-ols through the ring-opening aryl/alkylation of 7-oxabenzonorbornadiene derivatives. The chromium catalyst allowed the use of unstable aryl Grignard reagents with esters and N-protecting groups. In situ formed diarylchromate(I) from tetraarylchromate(III) was identified as the active species in this catalytic reaction based on control experiments.
Article
Chemistry, Organic
Angel Ho, Austin Pounder, Samuel Koh, Matthew P. Macleod, Emily Carlson, William Tam
Summary: This study demonstrates the ability of carboxylic acid tethered CPOBD to undergo ring-opening reactions under mild acidic conditions, with high regioselectivity towards type 3 ring-opened products. Substitution at specific positions of CPOBD was found to hinder the ring-opening reactions and decrease the yields of ring-opened products. Overall, this work represents the first examples of acid-catalyzed intramolecular ring-opening reactions of CPOBD with carboxylic acid nucleophiles.
SYNTHESIS-STUTTGART
(2022)
Article
Polymer Science
Salvatore Impemba, Gabriele Manca, Irene Tozio, Stefano Milione
Summary: In this study, new zinc catalysts were developed using thioether-amide ligands for the ring-opening polymerization of cyclic esters. Experimental and theoretical studies provided insights into the parameters that influence catalytic activity. The catalysts exhibited high activity in the polymerization of rac-beta-butyrolactone and showed agreement with expected results in terms of molecular weight and polydispersity index.
Article
Chemistry, Physical
Amit Singh Adhikari, Soumen Pandit, Ruchir Kant, Nilanjana Majumdar
Summary: An efficient method for highly selective allylic substitution of vinylcyclopropanes using carboxylic acids via iridium catalysis has been developed, providing a high yield of synthetically useful chiral building blocks. The practical application of the products in useful transformations demonstrates its utility.
Article
Polymer Science
Yi Wan, Yun Bai, Hai Xu, Jianghua He, Yuetao Zhang
Summary: The study successfully synthesized five chiral binuclear aluminum methyl complexes, which catalyze the ring-opening polymerization of rac-lactide in a controlled manner and produce polymers with high isoselectivity. The kinetic studies show a first-order dependence on monomer concentration, supporting an enantiomorphic site control mechanism for the catalysts. This strategy can also be applied to other lactones for ring-opening polymerization.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Peng Shan, Panpan Niu, Huifang Zhang, Chuanhao Zhang, Ningyue Lu, Yan Wang, Binbin Fan, Ruifeng Li
Summary: The Ir/H-SSZ-13 catalysts showed higher activity and yields in methylcyclopentane ring-opening reaction compared to other catalysts. Ir species supported on H-SSZ-13-A exhibited higher activity than those on H-SSZ-13-B, especially at low Ir loading. The presence of strong acid sites on the external surface of H-SSZ-13-A promoted the reactivity of Ir/H-SSZ-13-A, making it a potential catalyst for ring-opening reactions.
CATALYSIS COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Biao Wang, Han Zhong, Xu Tian
Summary: An efficient cascade reaction of cyclobutanones with chalcones has been developed, using inexpensive potassium tert-butoxide as a promoter. It enables the synthesis of densely substituted cyclohex-3-ene-carboxylic acids in high yields and with high diastereoselectivities, which are difficult to prepare using conventional methods. The method offers the advantages of transition-metal-free conditions, readily available starting materials, wide scope, and high atom economy.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Kohei Nishi, Hayato Tsurugi, Kazushi Mashima
Summary: Chromium(III) trichloride in combination with aryl/alkyl Grignard reagents exhibited high catalytic activity for the ring-opening arylation reaction of 7-oxabenzonorbornadiene derivatives, producing syn-2-aryl/alkyl-1,2-dihydronaphthalen-1-ols in high yields. The superior catalytic activity of the chromium catalyst allowed the use of unstable aryl Grignard reagents. Control experiments suggested that the in situ formed diarylchromate(I) served as the active species in the catalytic reaction.
Article
Chemistry, Physical
Sami Gesslbauer, George Hutchinson, Andrew J. P. White, Jordi Bures, Charles Romain
Summary: The research demonstrates that the activity of chiral-at-metal aluminum complexes in cyclic ester ring-opening polymerization is influenced by the alkoxide bulkiness and complex chirality. Experimental results show that using enantiopure catalysts can achieve better results than using a mixture of racemic catalysts.
Article
Chemistry, Physical
Chao-Wei Zhang, Xian-Qi Hu, Yuan-Hao Dai, Peng Yin, Chuanyong Wang, Wei-Liang Duan
Summary: The catalytic synthesis of P- and axially chiral biaryl phosphine oxides was achieved using Cp*Ir-catalyzed asymmetric C-H coupling, with the stereoselectivity controlled by chiral carboxylic amides. The transformation of products into chiral trivalent phosphine ligands was also demonstrated.
Article
Chemistry, Multidisciplinary
Erika Linde, Berit Olofsson
Summary: The diarylation and skeletal diversification of unstrained cyclic amines was explored to expand and modify their properties. A novel class of amino-substituted diaryliodonium salts was synthesized from cyclic amines and converted to highly functionalized diarylamines through a one-pot N-arylation/ring opening reaction. This strategy proved efficient in the late-stage functionalization of natural products and pharmaceuticals, and provided a wide variety of complex diarylamines. The method involves the introduction of two different aryl groups and the retention of an iodo-substituent, allowing for downfield diversification of the products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ying-Qiong Guo, Fan Chen, Chen-Liang Deng, Xing-Guo Zhang
Summary: This method allows for the simple and efficient synthesis of N-methyl-N-(o-methylthio)phenyl amides, featuring the direct construction of N-Me and S-Me bonds in a one-pot reaction through the decomposition of easily prepared benzothiazoles.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Pep Rojo, Medea Molinari, Albert Cabre, Clara Garcia-Mateos, Antoni Riera, Xavier Verdaguer
Summary: Chiral compounds containing nitrogen heteroatoms are crucial for the chemical, pharmaceutical, and agrochemical industries. In this study, a series of P-stereogenic phosphinooxazoline iridium catalysts were synthesized and successfully used in the asymmetric hydrogenation of N-Boc-2,3-diarylallyl amines, achieving high enantioselectivity. The synthetic utility of the obtained 2,3-diarylpropyl amines was also demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhaofeng Gao, Jingwen Liu, Haizhou Huang, Huiling Geng, Mingxin Chang
Summary: The research reports on efforts to merge two asymmetric reductive amination reactions into a single-step transformation, utilizing specific catalyst and acid additives to successfully synthesize enantiopure secondary amine products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Masaru Kondo, Kento Nakamura, Chandu G. Krishnan, Hiroaki Sasai, Shinobu Takizawa
Summary: This study presents recent advances in photoswitchable chiral organocatalysts and their applications in the photomodulation of enantioselective reactions. Under appropriate light irradiation, the E/Z-photoisomerization of the photoresponsive units on the catalysts controls the catalytic activity and/or selectivity of the reactions. The study also elucidates the design, synthesis, and catalytic application of azobenzene BINOL-based photoswitchable chiral phase-transfer catalysts. This account provides insights into the appropriate design of a photoswitchable chiral organocatalyst for achieving good enantioselectivity and photocontrol.
Review
Chemistry, Multidisciplinary
Ting Wu, Wenjun Tang
Summary: This Minireview summarizes recent progress on the synthesis of bridged polycyclic skeletons by transition-metal-catalyzed carbon-carbon bond-forming reactions, detailing four main ring-forming strategies.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Duanshuai Tian, Ronghua Xu, Jinbin Zhu, Jianxun Huang, Wei Dong, Jerome Claverie, Wenjun Tang
Summary: An efficient asymmetric hydroesterification of diarylmethyl carbinols has been developed using a Pd-WingPhos catalyst, resulting in a series of chiral 4-aryl-3,4-dihydrocoumarins with excellent enantioselectivities and good yields. The method features mild reaction conditions, a broad substrate scope, and low palladium loadings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Wei Tian, Bowen Li, Duanshuai Tian, Wenjun Tang
Summary: A palladium-catalyzed 2-alkylation of indoles with alpha-bromo esters using a P,P=O ligand has been developed. The method shows excellent regioselectivities, mild reaction conditions, and good functional group compatibility. Mechanistic studies indicate that the reaction proceeds through a radical pathway.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Organic
Zhenya Li, Ronghua Xu, Huichuang Guo, He Yang, Guangqing Xu, Enxue Shi, Junhua Xiao, Wenjun Tang
Summary: Highly enantioselective hydrogenation of (Z)-N-sulfonyl-α-dehydroamido boronic esters using a JosiPhos-type ligand is realized for the first time. This method enables the convenient synthesis of a series of enantio-enriched N-sulfonyl-α-amido boronic esters with good yields and excellent enantioselectivities (up to 99% ee).
Article
Chemistry, Multidisciplinary
Bowen Li, Bangke Luo, He Yang, Wenjun Tang
Summary: This study reports an efficient palladium-catalyzed Heck reaction for the synthesis of heterocycles with α-heteroaryl substitution. The method exhibits a broad substrate scope and excellent functional group compatibility. The use of a sterically bulky ligand containing an anthryl moiety is crucial for this transformation. Additionally, an asymmetric variant of the Heck reaction has been achieved, enabling the efficient asymmetric synthesis of (S)-nicotine and its analogues via a cationic palladium pathway.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Minghui Zhu, Peixin Wang, Qinglong Zhang, Wenjun Tang, Weiwei Zi
Summary: The aldol reaction is an important and versatile transformation in organic synthesis, but achieving stereoselectivity for the formation of diastereomeric products is challenging. In this study, a new catalytic system was developed to overcome the selectivity limitations of the reaction. Computational studies provided insights into the reaction mechanism and stereochemistry of the catalytic system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
He Yang, Wenjun Tang
Summary: In this paper, researchers have developed a general, efficient, and enantioselective synthesis of axially chiral biaryl structures with ortho sulfur or nitrogen substituents using asymmetric cross-coupling. The method shows excellent compatibility with various functional groups and structural features, allowing for the synthesis of diverse chiral biaryl structures with high synthetic value. The authors have also demonstrated the applicability of the method in the synthesis of bioactive molecules and chiroptical molecules with circularly polarized luminescence properties.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Zhangwei Huang, Xianhua Pan, Lei Guo, Wenjun Tang
Summary: A concise total synthesis method utilizing palladium-catalyzed dearomatization cyclization is reported for generating challenging steroid scaffolds. The synthesis of diverse 6,6,6,5-tetracyclic steroid cores is achieved through ligand and reaction condition control.
Article
Chemistry, Multidisciplinary
Jinbin Zhu, Zhenyue Li, Jiaqi Li, Duanshuai Tian, Ronghua Xu, Zhiyong Tan, Zhengwang Chen, Wenjun Tang
Summary: In this report, an efficient rhodium-catalyzed addition of arylboronic acids to N-heteroaryl ketones is established, affording a variety of valuable alpha-heteroaryl alcohols with excellent functional group compatibility. The employment of the WingPhos ligand containing two anthryl groups is crucial for this transformation.
Article
Chemistry, Organic
Ben Gao, Yuqi Chang, Wenjun Tang
Summary: In this study, a machine learning black-box model was built to predict the enantiomeric excess value of asymmetric transfer hydrogenation reactions. Molecular descriptors were extracted as features based on DFT calculations, which were then inputted into the machine learning model to calculate the enantiomeric excess value. The results showed that our model performed the best on this dataset, with a test-set root-mean-square error of 8.6 and a coefficient of determination R-2 of 0.86 compared to the experimental value. The model can be used for predicting the enantiomeric excess value for asymmetric transfer hydrogenation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Mingkang Zhou, Yaodong Lin, Xiao-Xuan Chen, Guangqing Xu, Lung Wa Chung, Wenjun Tang
Summary: We report the chiral diboron-templated asymmetric homocoupling of aryl alkyl ketimines, leading to the formation of chiral vicinal tetrasubstituted diamines with high enantioselectivities and good to high yields. This powerful and efficient reaction is achieved by rational design and engineering of chiral diborons, which participate in a [3,3]-sigmatropic rearrangement. DFT studies reveal that different conformational assembling strategies of chiral diborons ensure the excellent enantioselectivity in the tight concerted transition states.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jiawei Sun, Yuan Chen, Sherif Shaban Ragab, Wei Gu, Ziqiang Tang, Yuexun Tang, Wenjun Tang
Summary: In this study, an unsaturation-functionalization strategy was applied to address the C19-hydroxylation issue for efficient synthesis of polyhydroxylated steroids. The synthetic method featured an effective asymmetric dearomative cyclization and various reactions to introduce the polyhydroxy functionalities. Ultimately, the total synthesis of 19-hydroxysarmentogenin and ouabagenin was achieved, demonstrating the synthetic versatility and practicality of these polyhydroxylated steroids in the search for new therapeutic agents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Wen-Jun Tang, Shu-Min Dai, Yue Yuan, Shuai Wang, Yu-Peng He, Fang Yu
Summary: The direct methoxylation of substituted phenylalanines has been achieved through methoxyiminoacyl (MIA)-mediated Pd-catalyzed C-H functionalization, resulting in the efficient synthesis of diverse ortho-methoxylated phenylalanine derivatives in good to high yields. Kinetic isotope effect studies reveal that the oxhydryl cleavage step is the rate-limiting step. Computational data demonstrate that the manner in which methanol participates greatly influences the energy barriers of transition states during the C(sp2)-O formation stage, with stepwise deprotonation and reductive elimination being superior to concerted deprotonation-methoxylation.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Multidisciplinary
He Yang, Hanxiao Yu, Izabela A. Stolarzewicz, Wenjun Tang
Summary: In the past two decades, there has been a significant increase in the proportion of approved chiral drugs and drug candidates under medical studies. This has posed a challenge for medicinal and process chemists in efficiently synthesizing enantiopure pharmaceuticals. However, the development of asymmetric catalysis has provided an effective solution to this challenge, promoting drug discovery and industrial production of active pharmaceutical ingredients in an economic and environmentally friendly manner. This review summarizes the recent applications of asymmetric catalysis in the pharmaceutical industry, showcasing the achievements and trends in the asymmetric synthesis of therapeutic agents using state-of-the-art technologies.
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.
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
