Article
Chemistry, Organic
Julien Braire, Aurelie Mace, Rania Zaier, Marie Cordier, Joelle Vidal, Claudia Lalli, Arnaud Martel, Francois Carreaux
Summary: An improvement in the catalytic enantioselective allylboration of isatins with 2-allyl-1,3,2-dioxaborolane in the presence of chiral BINOL derivatives is reported, offering an efficient one-step access to enantioenriched N-unprotected 3-allyl-3-hydroxy-2-oxindoles. The origins of the high enantioselectivity and the key role of the alcohol additive have been investigated.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Julien Braire, Aurelie Mace, Rania Zaier, Marie Cordier, Joelle Vidal, Claudia Lalli, Arnaud Martel, Francois Carreaux
Summary: An improvement in the catalytic enantioselective allylboration of isatins with 2-allyl-1,3,2-dioxaborolane in the presence of chiral BINOL derivatives is reported. The high enantioselectivity of this reaction is due to the internal hydrogen bonding and the addition of alcohol additive, as shown by DFT calculations and kinetics study.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Laxman Devidas Khalse, Prasanta Ghorai
Summary: An efficient cascade protocol for the stereoselective synthesis of borylated carbocycles has been developed. This approach involves copper-catalyzed borylative Michael/Michael cyclization and allows the preparation of 24 new boronic ester substituted indanes, cyclohexanes, and cyclopentanes in good yields with excellent diastereoselectivities and functional group tolerance. The synthetic transformation of carbacyclic boronates was also successfully demonstrated, and gram-scale synthesis was carried out effectively.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xiang-Shuai Liu, Yao Li, Xin Li
Summary: A highly efficient asymmetric 1,2-allylation reaction of beta,gamma-unsaturated alpha-ketoesters was achieved using a Bi(OAc)(3)/chiral phosphoric acid catalyst system under mild conditions. Additionally, an asymmetric formal 1,4-allylation reaction was realized through a one-pot process, yielding homoallylic tertiary alcohols and gamma-allyl-alpha-ketoesters with good yields and excellent enantioselectivities. Density functional theory calculations were used to interpret the high enantioselectivity observed in the reactions.
Article
Chemistry, Physical
Jae Yeon Kim, Yea Suel Lee, Do Hyun Ryu
Summary: This study successfully developed a new method to achieve enantioselective radical reactions of alpha, beta-unsaturated carbonyl compounds using visible light irradiation. In this reaction system, the ternary EDA complex and chiral oxazaborolidinium ions as catalysts not only yielded products with high yields, but also achieved high enantioselectivities.
Article
Chemistry, Multidisciplinary
Matthias Peeters, Jonathan Decaens, Alois Fuerstner
Summary: Chiral [BiRh]-paddlewheel complexes empowered by London dispersion enable the generation of (trifluoromethyl)furfurylidene metal complexes from a bench-stable triftosylhydrazone precursor. These complexes undergo asymmetric [2+1] cycloadditions, providing optically active trifluoromethylated cyclopropane or -cyclopropene derivatives, which are important building blocks for medicinal chemistry and difficult to obtain in optically active form.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Yukun Zhao, Jingwen Xu, Hongbing Chen, Yi Xia, Lin Hu
Summary: A first iron-catalyzed oxophosphorylation reaction of styrene derivatives with dialkyl H-phosphonates under open air conditions is developed, leading to the formation of a range of previously underexplored α-substituted β-ketophosphonates. Additionally, a convenient one-pot procedure for the direct conversion of styrenes to α,β-unsaturated ketones is demonstrated, providing access to valuable products from simple starting materials.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Xiaoqiang Yan, Jijun Jiang, Jun Wang
Summary: In this study, an unusual class of planar-chiral rhodium catalysts bearing non-chiral Cp ligands was described. These catalysts are readily tunable and were successfully used in enantioselective C-H activation reactions, showing great potential in this field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Egor M. Larin, Alexa Torelli, Joachim Loup, Mark Lautens
Summary: The study demonstrates the utilization of the Bpin group as a pronucleophile to facilitate the assembly of cyclic carbamates, leading to the synthesis of a wide range of benzoxazinone scaffolds, including enantioselective outcomes. The method is efficient, scalable, and simple, showcasing its utility in the synthesis of useful scaffolds.
Article
Chemistry, Physical
Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: Enantioselective C-H functionalization is a powerful tool for synthesizing chiral molecules. The combination of high-valent group 9 metals with achiral Cp-x ligands and chiral carboxylic acids has shown promise in enabling selective cleavage and functionalization of enantiotopic C-H bonds. This Perspective provides a detailed summary of the background, catalyst design, applied reactions, and future directions in this field.
Article
Chemistry, Multidisciplinary
Soshi Nishino, Yuji Nishii, Koji Hirano
Summary: A copper-catalyzed reaction has been developed for the regio- and diastereoselective borylamination of alpha,beta-unsaturated esters with B(2)pin(2) and hydroxylamines. The reaction delivers acyclic beta-boryl-alpha-amino acid derivatives with high anti-diastereoselectivity, which is difficult to achieve using established methods. Furthermore, the use of a chiral phosphoramidite ligand allows for the enantioselective synthesis of optically active beta-borylated alpha-amino acids. The resulting products can be further transformed into beta-functionalized alpha-amino acids, which are of great interest in medicinal chemistry.
Article
Chemistry, Organic
Hiroki Murakami, Ayano Yamada, Kenichi Michigami, Yoshiji Takemoto
Summary: A novel method has been developed in this study for controlling carbonyl alpha-chirality and functionalizing beta-position through the conjugate addition-asymmetric protonation (CAAP) of alpha,beta-unsaturated carboxylic acids using chiral thiourea-amino boronic acid hybrid catalysts. This method is also applied in the asymmetric synthesis of biologically active compounds.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Chunhui Zhang, Jijun Jiang, Xiaoyu Huang, Jun Wang
Summary: A new type of CpRh(III) catalyst has been successfully designed and synthesized for asymmetric C-H activation. The catalyst, with prochiral tetrasubstituted Cp-px ligands, showed high catalytic activity in various reactions, achieving high yields and enantiomeric excesses.
Article
Chemistry, Multidisciplinary
Ken-Loon Choo, Bijan Mirabi, Karl Z. Demmans, Mark Lautens
Summary: Enantioenriched spiro-oxiranes with three contiguous stereocenters were synthesized using a rhodium-catalyzed cascade reaction, enabling the formation of a spirocyclic framework in a single step. Both sp(2)- and sp-hybridized carbon nucleophiles were found to be efficient initiators, yielding products with different functional groups. Derivatization studies demonstrated the synthetic versatility of the products' epoxide and alkyne moieties. DFT calculations were employed to explain spectroscopic discrepancies between solution- and solid-state structures of the products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yu-Yi Cheng, Wei-Sian Li, Hsyueh-Liang Wu
Summary: This paper introduces the development of new chiral bicyclo[2.2.1]heptadiene ligands for Rh-catalyzed asymmetric additions of various organoboron reagents to imine derivatives, leading to the formation of enantioenriched alpha-chiral amines. The transformation of the adducts into known natural products or molecules of pharmaceutical importance confirms the synthetic usefulness of this method.
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)