Article
Chemistry, Physical
Kai-Lin Yin, Shuang Zhao, Ying Qin, Shu-Han Chen, Bo Li, Dongbing Zhao
Summary: A carbon-to-silicon switch is widely used in drug discovery. However, organosilicon compounds are not naturally occurring, so the development of effective synthetic methods is crucial for expanding their diversity. In this study, we have successfully synthesized a chiral bridged bicyclic silicon scaffold, which provides a new approach for the synthesis of chiral silicon compounds.
Review
Chemistry, Organic
Cong-Cong Lu, Bo-Ya Hao, Ya-Ping Han, Yong-Min Liang
Summary: This article reviews the recent advances in the dearomative annulation of N-acylindoles with diverse nucleophiles since 2012, which can be classified into five categories: Dearomative Heck reactions, visible-light-induced reductive dearomatization, Lewis acid-catalyzed dearomative reductive reactions, asymmetric dearomative Heck reactions, and dearomative Heck reactions with other closely related N-acylindole reagents.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Senjie Ma, Haoyu Fan, Craig S. Day, Yumeng Xi, John F. Hartwig
Summary: Remote hydrofunctionalizations of alkenes enable the incorporation of functional groups distal to carbon-carbon double bonds. This study presents a system for the remote hydroamination of disubstituted alkenes, selectively functionalizing the subterminal, unactivated, methylene position of an alkyl chain. The high regioselectivity and reaction rates are attributed to the electronic properties of the amine substituent and the ligand DIP-Ad-SEGPHOS, which was developed by considering the steric and electronic effects of ligand modules. The remote hydroamination is compatible with a diverse range of alkenes and aminopyridines, allowing for the regioconvergent synthesis of amines from isomeric mixtures of alkenes. The resulting products can be further modified through nucleophilic aromatic substitution reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Maxwell B. Haughey, Kirsten E. Christensen, Darren L. Poole, Timothy J. Donohoe
Summary: The successful synthesis of the complex taiwanschirin fused [8,6,5] core, representing challenging and biologically active targets, was achieved through a novel alkynylation reaction and intramolecular Heck reaction method.
Article
Chemistry, Physical
Yoshinori Hashimoto, Shingo Harada, Ryosuke Kato, Kotaro Ikeda, Jannis Nonnhoff, Harald Groeger, Tetsuhiro Nemoto
Summary: This study reported a catalytic approach for the formal synthesis of more than 20 types of sarpagine/macroline alkaloids, with two key steps being the amide insertion reaction using cheap copper and biocatalytic asymmetric desymmetrization.
Article
Chemistry, Physical
Siqiang Fang, Zanjiao Liu, Hongkui Zhang, Jianke Pan, Yuan Chen, Xiaoyu Ren, Tianli Wang
Summary: The study presents an efficient and practical protocol for the direct enantioenrichment of free N-H sulfoximines. The method shows broad tolerability in desymmetrization and can easily be transformed into other classes of active sulfur-stereogenic compounds. Insights from mechanistic studies suggest a desymmetrization/KR synergic process with hydrogen-bonding interactions playing a key role in successful stereocontrol.
Article
Chemistry, Organic
Su Chen, Luc Van Meervelt, Erik V. Van der Eycken, Upendra K. Sharma
Summary: A mild visible-light-driven palladium-catalyzed radical tandem dearomatization reaction of indoles with unactivated alkenes is described. This reaction exhibited moderate to good yields and good to excellent diastereoselectivities. Under visible-light irradiation, a photo-excited state of the palladium complex was formed, which enabled the transfer of a single electron to N-(2-bromobenzoyl)indoles, leading to a hybrid palladium radical chemistry. This approach provides efficient and atom-economical access to diverse 2,3-disubstituted indoline derivatives.
Review
Chemistry, Multidisciplinary
Holly E. Bonfield, Damien Valette, David M. Lindsay, Marc Reid
Summary: This Minireview provides a timely summary of the development of palladium-catalyzed asymmetric redox-relay Heck-type processes, showcasing their importance in introducing remote stereocenters and applications in the pharmaceutical field. Additionally, a mechanistic summary, discussion on limitations, and outlook on future research directions are included to complement the overview.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Rui Chang, Yubing Pang, Juntao Ye
Summary: This study reports a photoinduced approach for hydroarylation of unactivated olefins using 4-hydroxycoumarins as the arylating reagent. The key to the success of this reaction is the conversion of nucleophilic 4-hydroxycoumarins into electrophilic carbon radicals through photocatalytic arene oxidation. This method not only overcomes the polarity-mismatch issue encountered under ionic conditions but also allows for a broad substrate scope and inhibits side reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jan Sietmann, Mike Ong, Christian Mueck-Lichtenfeld, Constantin G. Daniliuc, Johannes M. Wahl
Summary: Asymmetric access to gamma-lactams was achieved using (1S,2R)-1-amino-2-indanol for chiral induction, with downstream stereoinduction up to 88:12 dr. Mechanistic analysis revealed a Curtin-Hammett scenario, supported by spectroscopic, crystallographic, and computational studies. The method allows for the synthesis of optically pure gamma-lactams, including those with all-carbon quaternary stereocenters, and is exemplified by the formal synthesis of drug molecules baclofen, brivaracetam, and pregabalin.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Ashok Donthoju, Anandarao Munakala, Sushma Ellandula, Rambabu Chegondi
Summary: In this study, we have reported a palladium(0)-catalyzed decarboxylative oxa-Michael addition/remote alpha-allylation/1,3-migration reaction with high yields. The reaction is triggered by a base-mediated retro-Michael ring-opening reaction and subsequent syn-selective oxa-Michael addition.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kun-Long Song, Bin Wu, Wan-Er Gan, Yan Zeng, Yu-Jie Zhang, Jian Cao, Li-Wen Xu
Summary: We report a palladium-catalyzed coupling reaction that produces stereodefined silyl-enynes from alkynes and silicon electrophiles with high yields and highly stereoselective formation of either E- or Z-enynes depending on the choice of ligands.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Multidisciplinary
Jia-Qi Xie, Ren-Xiao Liang, Yi-Xia Jia
Summary: This review focuses on recent development of catalytic asymmetric Heck reaction and reductive Heck reaction, covering intermolecular and intramolecular versions since 2011. The article is organized in terms of the catalysts and olefin substrates, providing a clear structure for readers.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Kosuke Yamamoto, Keisuke Miyamoto, Mizuki Ueno, Yuki Takemoto, Masami Kuriyama, Osamu Onomura
Summary: In this study, glycerol was efficiently transformed into optically active monosulfonylated glycerol using a specific catalyst system. The synthetic utility of the monosulfonylated glycerol was demonstrated by its transformation into a C3 unit with differentially protected three hydroxy moieties.
Article
Chemistry, Organic
Yanting Li, Xiao-Yong Duan, Chengxian Yang, Yamei Wei, Jiahan Li, Xiaojie Ren, Jing Qi
Summary: This article describes a N-heterocyclic carbene-catalyzed atroposelective [3+3] annulation of enals with 2-aminomaleate derivatives. A series of substituted dihydropyridones with both C-N axis and point chirality were synthesized with good diastereo- and enantioselectivity under mild conditions. This efficient strategy introduces an additional point chiral element to an axial backbone, and the resulting structurally interesting atropisomers may have potential applications in drug discovery.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shenghan Teng, Zhiwei Jiao, Yonggui Robin Chi, Jianrong Steve Zhou
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Xiaolei Huang, Minh Hieu Nguyen, Maoping Pu, Luoqiang Zhang, Yonggui Robin Chi, Yun-Dong Wu, Jianrong Steve Zhou
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Xiaolei Huang, Shenghan Teng, Yonggui Robin Chi, Wenqiang Xu, Maoping Pu, Yun-Dong Wu, Jianrong Steve Zhou
Summary: The nickel-catalyzed intermolecular Heck reaction of cycloalkenes with aryl triflates, mesylates, and tosylates shows excellent enantiomeric ratios. Additionally, the asymmetric reductive Heck reaction is also applicable to a 2-cyclopentenone ketal, equivalent to conjugate arylation of the enone itself.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shenghan Teng, Yonggui Robin Chi, Jianrong Steve Zhou
Summary: Asymmetric coupling efficiently occurs between propargylic acetates, cycloalkenes, and electron-rich heteroarenes, yielding 2,3-disubstituted tetrahydrofurans and pyrrolidines in trans configuration with excellent enantiomeric ratios. The reaction proceeds via Wacker-type attack of nucleophilic heteroarenes on alkenes activated by allenyl Pd-II species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Daoyong Zhu, Wenqiang Xu, Maoping Pu, Yun-Dong Wu, Yonggui Robin Chi, Jianrong Steve Zhou
Summary: This study revealed that palladium catalyzes a domino Heck arylation and alkylation of nonconjugated cyclodienes to produce trans isomers of disubstituted cyclohexenes with exceptionally high enantiomeric ratios. Through DFT calculations and experiments, it was demonstrated that the interaction between the two CF bonds of Josiphos and the sodium ion of malonates facilitates stereoselective allylic attack. This represents a new type of attractive noncovalent interactions discovered in organometallic catalysis.
Article
Chemistry, Multidisciplinary
Peng Yang, Yaxin Sun, Kaiyue Fu, Li Zhang, Guang Yang, Jieyu Yue, Yu Ma, Jianrong Steve Zhou, Bo Tang
Summary: A nickel-catalyzed domino hydrocarboxylation-transfer hydrogenation reaction was utilized to convert terminal alkynes to alpha-chiral carboxylic acids. The reaction showed high selectivity and efficiency in preparing biologically active compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Shenghan Teng, Jianrong Steve Zhou
Summary: This review summarizes the recent advances in transition metal-catalyzed asymmetric alkylation of heteroarenes using alkenes, covering literature from 2000 to late 2021. The reactions are classified into different categories based on the metal-mediated substrate activation, and the corresponding reaction mechanisms and catalyst design are discussed.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Organic
Huihui Shao, Yao Zhao, Shuangqiang Wang, Rizhi Chen, Jianrong Steve Zhou, Xiaojin Wu
Summary: This study developed a Pd-catalyzed chemo- and regiocontrollable 1,1-diarylation reaction that allows for the reaction of unactivated aliphatic alkenes with two aryl halides. In this process, the first aryl insertion reaction involves beta-H elimination, while the second aryl insertion reaction is terminated by C-H bond formation.
Article
Chemistry, Multidisciplinary
Jianrong Steve Zhou, Luoqiang Zhang, Xiuhua Wang, Maoping Pu, Caiyou Chen, Peng Yang, Yun-Dong Wu, Yonggui Robin Chi
Summary: Nickel catalysts with chiral pyrox ligands were used for enantioselective reductive arylation and heteroarylation of aldimines using (hetero)aryl halides and sulfonates. Crude aldimines generated from the condensation of aldehydes and azaaryl amines can also be used for catalytic arylation. The mechanism involves an elementary step of 1,4-addition of aryl nickel(I) complexes to N-azaaryl aldimines, as supported by density functional theory (DFT) calculations and experiments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yao Zhao, Shuangqiang Wang, Huihui Shao, Xuyong Tan, Rizhi Chen, Teck-Peng Loh, Jianrong Steve Zhou, Xiaojin Wu
Summary: Pd-catalyzed double Heck reaction enables regioselective 1,1-diarylation of unactivated aliphatic alkenes. The trans addition of the second aryl rings to aliphatic chains in the main olefinic isomers suggests a mechanism involving two consecutive Heck arylations at the terminal carbons.
Article
Chemistry, Multidisciplinary
Zhaoming Ma, Wenqiang Xu, Yun-Dong Wu, Jianrong Steve Zhou
Summary: Cobalt complexes of chiral pyrox ligands are used as catalysts for the enantioselective reductive coupling of nonconjugated iododienes with aryl iodides or alkenyl bromides. This reaction enables the stereoselective synthesis of 5-7-membered azacycles carrying quaternary stereocenters. Mechanistically, the selectivity of cross-electrophile coupling comes from the selective coupling of alkylcobalt(I) complexes generated after cyclization with aryl iodides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Luoqiang Zhang, Dao-Yong Zhu, Jingyao Hu, Minjun Feng, Tze Chien Sum, Haoran Sun, Hajime Hirao, Yonggui Robin Chi, Jianrong Steve Zhou
Summary: In this study, direct alkylation of 5- and 6-membered heteroarenes, including azoles and azines, was achieved using alkanes, ethers, and carbamates under LED irradiation. Through the discovery of an organic photosensitizer, 9,10-dichloroanthracene, the overall efficiency of radical couplings was significantly increased via energy transfer of exciplexes, enabling successful oxidative couplings even with 1.5 equivalents of alkanes.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Zhaoming Ma, Lantian Sun, Jianrong Steve Zhou
Summary: The catalytic enantioselective domino alkenylation-heteroarylation reaction of nonconjugated iododienes shows excellent stereoselectivity and a wide range of substrate adaptability. The reaction enables the stereoselective synthesis of substituted azacycles carrying new quaternary stereocenters, such as piperidine, pyrrolidine azepine, and dihydropyrans. Mechanistically, the C-H bonds of heterocycles are activated by lithium alkoxides through reversible deprotonation, rather than conventional palladium(ii)-assisted metalation processes. Various types of heteroarenes can be used, including not only azoles (such as thiazoles, oxazoles, imidazoles, and oxadiazoles) but also nonazoles (thiophene, furan, and azine N-oxides).
Article
Chemistry, Multidisciplinary
Jianrong Steve Zhou, Siyu Guo, Xiaohu Zhao, Yonggui Robin Chi
Summary: Nickel complexes ligated by strongly donating diphosphines catalyze enantioselective hydrogenation for the preparation of acyclic and cyclic beta-amido esters, with a combination of acetic acid and indium powder providing protons and electrons to form nickel hydrido complexes under umpolung hydrogenation conditions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Jianrong Steve Zhou, Xiaolei Huang, Shenghan Teng, Yonggui Robin Chi
Summary: Nickel-catalyzed Heck reaction of cycloalkenes produces unusual conjugated arylated isomers. The omission of bases allows nickel hydride species to perform in situ olefin isomerization of initial Heck adducts, enhancing the reactivity of aryl triflates, mesylates, tosylates, and pivalates.
CHEMICAL COMMUNICATIONS
(2021)
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)
