Article
Chemistry, Organic
Shuangshuang Li, Ju Qiu, Bowen Li, Zuolian Sun, Peizhong Xie, Teck-Peng Loh
Summary: A practical palladium/calcium catalytic system was developed for dehydrative allylation with unactivated allylic alcohols, utilizing ethanol solvent with a water additive to accelerate proton transfer. This system allowed for smooth reactions at room temperature, producing allylic compounds with a variety of functional groups in high to excellent yields.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Cristiana Margarita, Davide Di Francesco, Hernando Tunon, Ivan Kumaniaev, Carlos Jansson Rada, Helena Lundberg
Summary: This study describes the direct etherification of wheat straw lignin and lignin model compounds using alcohols as reagents and zirconocene triflate as a moisture-tolerant Lewis acidic catalyst. The reaction proceeded under mild conditions without the need for water-scavenging techniques, resulting in the formation of a variety of ethers derived from lignin models with synthetic handles relevant for thermoset applications. The application of this protocol on wheat straw-derived lignin also demonstrated the first example of metal-catalyzed direct benzylic allylation of lignin using allyl alcohol as a reagent.
Article
Chemistry, Organic
Suvi Holmstedt, Alexander Efimov, Nuno R. Candeias
Summary: The ease of O,O-silyl group migrations on a quinic acid-derived cyclitol was found to depend on the silicon substituents and reaction conditions. Improvements in conditions were observed to enhance the formation of the main isomer, which could be used in the formal synthesis of a vitamin D receptor modulator and in the total synthesis of a metabolite from the African ant Crematogaster nigriceps.
Article
Engineering, Chemical
Jiale Wu, Yuan Tao, Dang Cheng, Fener Chen
Summary: In this study, a hybrid microflow system composed of a coaxial double-tube microreactor and a capillary microreactor was developed for the selective borohydride reduction of α,β-unsaturated esters to allylic alcohols. The system achieved complete conversion of methyl cinnamate to cinnamyl alcohol with up to 85% yield under optimized conditions. The kinetics of the reduction reaction were examined and modeled, providing insights into the reaction behavior and performance of the hybrid microflow process.
CHEMICAL ENGINEERING SCIENCE
(2023)
Article
Chemistry, Organic
Jiahao Liu, Shidong Zhang, Zihong Luan, Yan Liu, Zhuofeng Ke
Summary: A simplified catalytic system has been developed to efficiently catalyze the selective dehydrogenation of allyl alcohol to form alpha,beta-unsaturated carbonyls without the use of additional oxidants or H-2 acceptors.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Georgios Toupalas, Loelie Ribadeau-Dumas, Bill Morandi
Summary: Oxygenated molecules are widely present in nature and artificial settings, and the redox transformation of C-O bonds is crucial for their processing. However, the use of traditional (super)stoichiometric redox agents poses practical challenges due to safety hazards and waste management requirements. In this study, we present a mild Ni-catalyzed fragmentation strategy based on carbonate redox tags, which enables redox transformations of oxygenated hydrocarbons without the need for external redox equivalents or additives. The catalytic process allows for the hydrogenolysis of strong C(sp(2))-O bonds and the catalytic oxidation of C-O bonds under mild conditions. The work demonstrates the potential of redox tags for organic synthesis.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Masahiro Sai, Hiroaki Kurouchi
Summary: In this study, the first KHMDS-catalyzed Michael additions of allylic alcohols to alpha,beta-unsaturated amides were reported. The reaction proceeds smoothly with only 5 mol% of KHMDS to afford a variety of 1,5-ketoamides in high yields. Mechanistic investigations revealed that the in-situ generation of the enolate from the allylic alcohol through a tunneling-assisted 1,2-hydride shift is crucial for the success of this transformation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Christianah Aarinola Akinnawo, Ndzondelelo Bingwa, Reinout Meijboom
Summary: Mesoporous zirconia doped with Cr exhibited outstanding reactivity and 100% selectivity in the Meerwein-Ponndorf-Verley reduction, mainly due to the intrinsic properties of its surface mesostructure rather than specific surface area. The synergistic effect between Cr and Zr species in the binary oxide facilitated the Lewis acidity-induced performance of the Cr_ZrO2 catalyst, showcasing its innovative application in the green synthesis of unsaturated alcohols.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jayabrata Das, Wajid Ali, Animesh Ghosh, Tanay Pal, Astam Mandal, Chitrala Teja, Suparna Dutta, Rajagopal Pothikumar, Haibo Ge, Xinglong Zhang, Debabrata Maiti
Summary: Transition metal catalysis plays a crucial role in activating unreactive C-H bonds. However, selectively activating distal aliphatic C-H bonds without directing templates is highly challenging. In this study, we demonstrated the activation of a methylene C-H bond in the presence of methyl C-H bonds to form unsaturated bicyclic lactones. This method enables the reversal of general selectivity in aliphatic C-H bond activation and simplifies the synthesis of important bicyclic lactones found in natural products and pharmaceuticals.
Article
Chemistry, Organic
Qiulin You, Xin Xiao, Yang Shi, Yimin Wu, Guangying Tan
Summary: This study reveals a novel iron-catalyzed para-C-H allylation reaction of aniline derivatives via a chelation-induced strategy, providing various allylic arenes with good yields and selectivity.
Article
Chemistry, Organic
Qiulin You, Xin Xiao, Yang Shi, Yimin Wu, Guangying Tan
Summary: Transition-metal-catalyzed directed C-H allylation of arenes is an efficient method to construct value-added allylic arenes. This study presents a novel iron catalyst and a chelation-induced strategy for the para-C-H allylation of aniline derivatives, which provides good yields and excellent selectivity.
Article
Chemistry, Multidisciplinary
Daisuke Uraguchi, Kohsuke Kato, Takashi Ooi
Summary: An o-quinone methide (o-QM) with an overcrowded olefinic framework is introduced, showing dehydridation activity due to its enhanced zwitterionic character, especially under photoexcitation. Experimental analysis and density functional theory calculations provide mechanistic insights, revealing that the o-QM operates in dehydridative catalysis for the oxidation of benzylic secondary alcohols.
Article
Chemistry, Organic
Ming Chen, Yang Li, Zheng-Hui Guan
Summary: In this work, a palladium-catalyzed hydroalkoxycarbonylation and hydroxycarbonylation of cyclopent-3-en-1-ols is reported, which enables the synthesis of bridged bicyclic lactones and beta,gamma-unsaturated carboxylic acid. The reactivity of cyclopent-3-en-1-ols is controlled by the palladium catalyst and ligands. The reaction is additive-free and exhibits a broad substrate scope, allowing access to valuable synthetic and medical intermediates.
Article
Chemistry, Organic
Juan A. Rivas-Loaiza, Aneta Baj, Yliana Lopez, Stanislaw Witkowski, Agnieszka Wojtkielewicz, Jacek W. Morzycki
Summary: The paper presents a simple synthesis method of Demissidine stereoisomers and analogues from a common steroidal sapogenin tigogenin. Different stereoisomers and compounds were obtained through step-by-step transformation or direct reductive amination in the synthesis process.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jonathan Z. Z. Shezaf, Catherine G. G. Santana, Connor Saludares, Edward S. S. Briceno, Ken Sakata, Michael J. J. Krische
Summary: The first correlation between metal-centered stereogenicity and regio-selectivity in a catalytic process is described. Alternate pseudo-diastereomeric chiral-at-ruthenium complexes of the type RuX(CO)[& eta;(3)-prenyl][(S)-SEGPHOS] form in a halide-dependent manner and display divergent regio-selectivity in catalytic C-C couplings of isoprene to alcohol proelectrophiles via hydrogen autotransfer. Control of metal-centered diastereo-selectivity has unlocked the first catalytically enantio-selective isoprene-mediated carbonyl tert-prenylations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
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)