Article
Chemistry, Multidisciplinary
Sheng-Qiang Lai, Bang-Yi Wei, Jia-Wei Wang, Wei Yu, Bing Han
Summary: A tunable photocatalytic method using ketoxime carbonates as reagents has been developed for anti-Markovnikov hydro- and aminooxygenation of unactivated alkenes. The reaction is initiated by N-O bond homolysis of ketoxime carbonates under visible-light photocatalysis, followed by generation of alkoxylcarbonyloxyl and iminyl radicals leading to carbon radical addition to alkenes. The carbon radical can either abstract a hydrogen atom to form hydrooxygenation product or be trapped by iminyl radical to yield aminooxygenation product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Sen Yang, Hao Hu, Ming Chen
Summary: A highly efficient visible-light-induced elimination method for alkyl halides is presented, which selectively yields unactivated terminal olefins vital in organic synthesis.
Article
Chemistry, Organic
Sen Yang, Hao Hu, Ming Chen
Summary: A highly efficient method for visible-light-induced regio- and chemoselective elimination of alkyl halides yielding unactivated terminal olefins vital in organic synthesis is presented. The reaction, achieved through ligand control, exhibits remarkable regioselectivity and suppresses undesired side reactions, particularly 1,5-hydrogen atom transfer (HAT). This method favors primary alkyl halides while preserving secondary and tertiary alkyl bromides, thereby enabling the incorporation of terminal olefins in complex molecules for late-stage functionalization.
Article
Chemistry, Organic
Muyang Yang, Wen Shao, Lin Zuo, Jiajia Wang, Yongzhuo Xu, Guojiang Mao, Guo-Jun Deng
Summary: A metal-free, highly site-selective trifluoromethylaminoxylation of activated and unactivated olefins was developed, allowing direct access to diverse β-trifluoromethyl trisubstituted hydroxylamines, tertiary alcohols, isoxazolines, isoxazolidines, and amino alcohols. The reaction proceeds through a SET process between hydroxylamine and a hypervalent iodine-CF3 reagent, generating two free radicals for regio- and diastereoselective addition to alkenes. The synthetic potential of the method was demonstrated through the late-stage functionalization of the products and various postreaction modifications.
Article
Chemistry, Multidisciplinary
Keitaro Matsuoka, Narumi Komami, Masahiro Kojima, Tsuyoshi Mita, Kimichi Suzuki, Satoshi Maeda, Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: In this study, a novel method for chemoselective cleavage of unactivated tetraalkylsilanes under mild conditions using iodine tris(trifluoroacetate) was reported. The reaction enables subsequent synthetic reactions and provides highly stable synthetic precursors for organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Peng Wang, Honghai Zhang, Mingqi Zhao, Shuangshuang Ji, Lu Lin, Na Yang, Xingliang Nie, Jinshuai Song, Saihu Liao
Summary: A new method based on radical fluorosulfonylation has been developed for the synthesis of aliphatic sulfonyl fluorides from unactivated alkenes. This method can be applied to the late-stage modifications of natural products and peptides, as well as drug ligation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Chenxiao Qi, Guillaume Force, Vincent Gandon, David Leboeuf
Summary: A novel method for haloamidation is introduced in this paper, providing new building blocks for drug discovery. This method overcomes some limitations of traditional reactions and the reaction mechanism is deeply studied, which is expected to promote the development of more complex transformations in this field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yang Yuan, Youcan Zhang, Wenbo Li, Yanying Zhao, Xiao-Feng Wu
Summary: A novel method for constructing amide bonds through anti-Markovnikov hydroaminocarbonylation of unactivated alkenes has been developed. Copper catalysis, hydroxylamine electrophile reagents, and poly(methylhydrosiloxane) (PMHS) were used under mild conditions. The reaction showed a high degree of tolerance towards various functional groups and efficiently converted unactivated terminal alkenes, 1,1-disubstituted alkenes, and cyclic alkenes to the corresponding amides with exclusive anti-Markovnikov selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yang Yuan, Youcan Zhang, Wenbo Li, Yanying Zhao, Xiao-Feng Wu
Summary: This paper reports a general method for the anti-Markovnikov hydroaminocarbonylation of unactivated alkenes under mild conditions, using copper catalysis in combination with hydroxylamine electrophile reagents and poly(methylhydrosiloxane) (PMHS) as a cheap and environmentally friendly hydride source. The reaction tolerates a variety of functional groups and efficiently converts unactivated terminal alkenes, 1,1-disubstituted alkenes, and cyclic alkenes to the corresponding amides with exclusive anti-Markovnikov selectivity (and high enantioselectivities/diastereoselectivities). Additionally, with minimal modification of the reaction conditions, alkynes can also undergo tandem hydrogenation-hydroaminocarbonylation to alkyl amides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Rahul K. Shukla, Atul K. Chaturvedi, Chandra M. R. Volla
Summary: A Pd(II)-catalyzed directed, regio-controlled hydroheteroarylation of unactivated alkenes has been developed for the construction of gamma-heteroaryl-substituted carbonyl compounds. The methodology is operationally simple and compatible with a variety of nucleophiles to deliver structurally divergent heterocyclic skeletons. This approach also demonstrated synthetic utility in gram-scale synthesis, directing group removal, and late-stage modification of drugs and natural products.
Article
Chemistry, Multidisciplinary
Henry Lindner, Willi M. Amberg, Erick M. Carreira
Summary: In this study, unactivated olefins are converted into alkyl azides using bench-stable NaN3 in the presence of FeCl3·6H2O under blue-light irradiation. The reaction exhibits anti-Markovnikov selectivity and can be conducted under mild ambient conditions in the presence of air and moisture.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Yali Zhou, Xingjun Xu, Hongwei Sun, Guanyu Tao, Xiao-Yong Chang, Xiangyou Xing, Bo Chen, Chen Xu
Summary: This study reports effective platinum catalysts for hydroalkoxylation and hydroamination of unactivated alkenes, accommodating various alkene substitution patterns and providing a foundation for rational design of chiral catalysts through detailed mechanistic investigations.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Tao Song, Kuiyang Wang, Qianjia Yuan, Wanbin Zhang
Summary: This study reports the nickel-catalyzed hydroamination and hydroalkoxylation reactions between unactivated amines and alcohols with enolactams. The method demonstrates good functional group tolerance and delivers the corresponding hydrofunctionalized products in good to excellent yields (& LE;98%). Additionally, an intramolecular hydroalkoxylation of an enolactam is successfully achieved, providing a cyclization product in good yield. Mechanistic studies reveal that tBuI plays crucial roles as a hydride donor and radical precursor for the reaction's success.
Article
Nanoscience & Nanotechnology
Chloe A. Ramsperger, Noah Q. Tufts, Ankit K. Yadav, Jacob M. Lessard, Kyriakos C. Stylianou
Summary: In this study, the metal-organic framework Cr-MIL-101-SO3H was used as a catalyst for the facile synthesis of eight alpha-aminonitriles, five of which are reported as new molecules. The catalytic reaction is conducted under solvent-free conditions at room temperature, with a low loading of the catalyst. Additionally, the catalyst exhibits a high degree of chemoselectivity and can be applied to substrates with sterically hindered and electronically withdrawn functional groups.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Yinsong Zhao, Shaozhong Ge
Summary: The structural diversity of sp(3)-triorganometallic reagents enhances their potential in modular construction of molecular complexity in chemical synthesis. We report a selective triborylation reaction of unactivated alkenes to access synthetically versatile 1,1,3-triborylalkanes. This reaction provides a general platform for regioselective trifunctionalization of unactivated alkenes, and its utility is highlighted by the synthesis of various value-added chemicals from readily accessible unactivated alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Jun Kee Cheng, Shao-Hua Xiang, Shaoyu Li, Liu Ye, Bin Tan
Summary: Atropisomerism is a stereochemical behavior exhibited by three-dimensional molecules with rotationally restricted sigma bonds, and compounds with atropisomerically chiral properties are increasingly utilized in fields where molecular asymmetry is influential. There is a steady demand for atroposelective synthesis, leading to conceptually novel and streamlined methods for expanding the structural diversity of atropisomers. This review summarizes key achievements in the stereoselective preparation of biaryl, heterobiaryl, and nonbiaryl atropisomers between 2015 and 2020, emphasizing synthetic strategies for each structural class and potential applications of atropochiral targets.
Article
Chemistry, Multidisciplinary
Jian Zhang, Jun Wei, Wei-Yi Ding, Shaoyu Li, Shao-Hua Xiang, Bin Tan
Summary: Pnictogen-bonding catalysis based on sigma-hole interactions has been the focus of attention for synthetic chemists. A novel chiral antimony cation/anion pair was utilized to catalyze the enantioselective transfer hydrogenation of benzoxazines with remarkable efficiency and enantiocontrol potency even at 0.05 mol % loading. Investigation into the properties of the catalyst and mechanistic insights were conducted through nonlinear effect studies, 1H NMR, LC-MS, and control experiments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Peng-Ying Jiang, Kai-Fang Fan, Shaoyu Li, Shao-Hua Xiang, Bin Tan
Summary: The authors present a metal-free oxidative cross-coupling reaction between isoquinolines and 2-naphthols to efficiently access the QUINOL scaffolds. This approach addresses the challenge of high production costs and limited synthetic methods, providing a new strategy for asymmetric catalysis. The study demonstrates the significance of QUINOL as a key platform molecule for the development of chiral ligands and catalysts in asymmetric catalysis.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Qian-Jin An, Wang Xia, Wei-Yi Ding, Huan-Huan Liu, Shao-Hua Xiang, Yong-Bin Wang, Guofu Zhong, Bin Tan
Summary: This study presents a strategy for the synthesis of axially chiral N-arylbenzimidazoles using chiral phosphoric acid catalysis, demonstrating excellent chemo- and regioselectivity as well as high levels of enantiocontrol. The nitroso group plays a unique role in the domino reaction, acting as a linchpin to facilitate C-N bond formation and oxidative aromatization. The resulting atropisomeric products can be further elaborated to produce axially chiral derivatives for potential applications in asymmetric catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Wang Xia, Zi-An Zhou, Jie Lv, Shao-Hua Xiang, Yong-Bin Wang, Bin Tan
Summary: A new organocatalytic approach was developed for the synthesis of N-naphthyl phenothiazine and phenoxazine scaffolds through azo-group enabled C-H amination of arenes. This reaction showcased operational simplicity, substrate generality, and excellent functional group compatibility, with the catalyst efficiency preserved after 5 catalytic cycles.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Jun Kee Cheng, Shao-Hua Xiang, Bin Tan
Summary: This paper describes the strategies to address the challenges in efficient synthetic access and skeletal variety within the organocatalytic context. The approaches include modulating nucleophilicity, designing electron-withdrawing activating groups, and using electrophilic arene precursors for arylation. These strategies have led to the synthesis of structurally diverse axially chiral compounds.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Shi-Jiang He, Shuai Zhu, Sheng-Qi Qiu, Wei-Yi Ding, Jun Kee Cheng, Shao-Hua Xiang, Bin Tan
Summary: This study discovered a novel type of axially chiral anthrone-derived skeleton by introducing axial chirality on symmetric anthrone skeletons through stereoselective condensation. The enantioenriched anthrones could be further transformed into dibenzo-fused seven-membered N-heterocycles with well-defined stereogenic center via Beckmann rearrangement.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Pengquan Chen, Mei-Jun Lv, Jun Kee Cheng, Shao-Hua Xiang, Xiang-Zhong Ren, Junmin Zhang, Bin Tan
Summary: Azonaphthalenes have been confirmed as effective arylation reagents for various asymmetric transformations. In this study, a highly efficient approach to form triaryl-substituted all-carbon quaternary stereocenters through chiral phosphoric acid-catalyzed enantioselective arylation of 3-aryl-2-oxindoles with azonaphthalenes is revealed. This chemistry is scalable and demonstrates excellent functional group tolerance, providing a series of 3,3-disubstituted 2-oxindole derivatives in good yields with excellent enantiocontrol.
Article
Chemistry, Multidisciplinary
Peng-Ying Jiang, San Wu, Guan-Jun Wang, Shao-Hua Xiang, Bin Tan
Summary: QUINAPs have been widely used in enantioselective transformations, but their limited substrate range and high cost hinder their broader application. In this study, we report the first atroposelective oxidation of an N atom using a chiral ketone catalyst, allowing the kinetic resolution of QUINAPOs with excellent enantioselectivity. The enantioenriched products can be easily converted into the desired QUINAP targets without loss of stereochemical integrity. Mechanistic investigations reveal the involvement of a dioxirane as the active catalytic species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ming Wu, Yi-Wei Chen, Qian Lu, Yong-Bin Wang, Jun Kee Cheng, Peiyuan Yu, Bin Tan
Summary: A highly efficient method for the synthesis of atropisomers through functionalization of the Si-C bond between dinaphthosiloles and silanol nucleophiles was presented. The versatile nature of the Si-C bond allows for the facile derivatization of chiral products into other functional atropisomers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Si-Li Lin, Ye-Hui Chen, Huan-Huan Liu, Shao-Hua Xiang, Bin Tan
Summary: In this study, chiral cyclobutene units were synthesized using bicyclo[1.1.0]butanes for the first time, offering an efficient and asymmetric route with good regio- and enantiocontrol. Control experiments verified the formation of a key carbocation intermediate at the benzylic position.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ye-Hui Chen, Meng Duan, Si-Li Lin, Yu-Wei Liu, Jun Kee Cheng, Shao-Hua Xiang, Peiyuan Yu, Kendall N. Houk, Bin Tan
Summary: This article introduces an effective strategy for umpolung functionalization of imines through aromatization. The attachment of strongly electron-withdrawing groups to imines enhances their reactivity, enabling direct amination of (hetero)arenes. Additionally, the use of chiral catalysts allows for the synthesis of (hetero)aryl C-N atropisomers or enantioenriched aliphatic amines.
Article
Chemistry, Multidisciplinary
Peng-Ying Jiang, San Wu, Guan-Jun Wang, Shao-Hua Xiang, Bin Tan
Summary: QUINAPs are a crucial class of chiral compounds that have remarkable features in stereoinduction. However, their restricted substrate range and expensive price limit their broader utilization. In this study, the first atroposelective oxidation of an N atom using a chiral ketone catalyst was described, allowing the kinetic resolution of QUINAPOs with excellent enantioselectivity. Mechanistic investigations revealed the role of a dioxirane as the active catalytic species. The developed protocol has practicality and can be applied in enantioselective transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ming Wu, Yi-Wei Chen, Qian Lu, Yong-Bin Wang, Jun Kee Cheng, Peiyuan Yu, Bin Tan
Summary: Chiral organosilanes are important chemical entities in the development of functional organic materials, asymmetric catalysis, and medicinal chemistry. An efficient method for atroposelective synthesis of biaryl siloxane atropisomers via organocatalytic Si-C bond functionalization of dinaphthosiloles with silanol nucleophiles is presented. The reaction proceeds through an asymmetric protonation and simultaneous Si-C bond cleavage/silanolysis sequence in the presence of a newly developed chiral Bronsted acid catalyst. The versatile nature of the Si-C bond expands the applicability of this method.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Heng-Hui Li, Shaoyu Li, Jun Kee Cheng, Shao-Hua Xiang, Bin Tan
Summary: An efficient photocatalytic system for obtaining functionalized N-heterobiaryls under mild conditions is described, suitable for gram-scale synthesis. The method demonstrates practicality and accessibility using commercially available starting materials.
CHEMICAL COMMUNICATIONS
(2022)
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)
