Article
Chemistry, Organic
Nuria Vazquez-Galinanes, Isabel Velo-Heleno, Martin Fananas-Mastral
Summary: A method for the use of vinyl epoxides in catalytic allylboration of alkynes is described, which allows for the synthesis of bifunctional skipped dienes bearing both an allylic alcohol and an alkenylboronate from simple starting materials with high regio- and stereoselectivity. These products show versatile reactivity and can be converted into cyclic boron compounds and polyenes.
Article
Chemistry, Organic
Xing-Long Zhang, Rui-Li Guo, Meng-Yue Wang, Bao-Yin Zhao, Qiong Jia, Jin-Hui Yang, Yong-Qiang Wang
Summary: The unprecedented palladium-catalyzed three-component dehydrogenative cascade coupling method introduces a C5 structural unit into indoles with high selectivity and a broad substrate scope, making it an economical and efficient approach.
Article
Chemistry, Multidisciplinary
Xingben Wang, Frederic W. Patureau
Summary: The highly selective synthesis of mono- and di-2-fluoroallylic amines from gem-difluorocyclopropanes and primary anilines using a Pd catalyst is described. Initial kinetic studies suggest a first order reaction with the gem-difluorocyclopropane substrate and a zeroth order reaction with the aniline coupling partner. The newly synthesized fluoroallylic motifs have important applications in synthetic and medicinal chemistry, and can potentially stimulate the development of coupling methods using strained cyclic building blocks.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Jake J. Blackner, Deirdre M. Rooney, Joshua W. Hollett, J. Adam McCubbin
Summary: A boronic acid catalyzed carbon-carbon and carbon-nitrogen bond-forming reaction using ferrocenium boronic acid hexafluoroantimonate salt as catalyst has been developed for the functionalization of various pi-activated alcohols. The reaction proceeds under mild conditions and yields up to 98%, with higher yields and selectivity observed when using organosilane nucleophiles. Computational studies provide a mechanistic pathway for the retention of E/Z stereochemistry when using alkenyl silanes as nucleophiles. This methodology is effective with a variety of organosilane nucleophile sub-types, including allylic, vinylic, and propargylic trimethylsilanes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Sardaraz Khan, Tauqir Ahmad, Tahir Rasheed, Nisar Ullah
Summary: Vinylethylene carbonates (VECs) are diverse and functionalized structural frameworks that can undergo transitional metal-catalyzed decarboxylative process to generate p-allyl-Pd intermediate, which in turn can react with a broad range of carbon and hetero nucleophiles to afford highly stereoselective construction of C-C and C-Het (N, O, S) bonds. The recent advances and applications of VECs in palladium-catalyzed allylic substitution and decarboxylative annulation reactions are reviewed and discussed in this article. These synthetic methods provide direct access to versatile building blocks, crucial in modern synthetic and medicinal chemistry.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Organic
Dustin D. Youmans, Hai N. Tran, Levi M. Stanley
Summary: Nickel-catalyzed isomerizations of homoallylic alcohols and a bishomoallylic alcohol proceed efficiently without the need for an exogenous ligand. The corresponding ketones are obtained in high yields (≤98%).
Article
Chemistry, Multidisciplinary
Ledan Zhou, Ding Liu, Huashan Huang, Ke Zhang, Yingtang Ning, Fen-Er Chen
Summary: We present a general method for synthesizing highly functionalized (Z)-allylic amines through decarboxylative allylation of vinyloxazolidin-2-ones. This process utilizes sodium sulfinates as nucleophiles to form a new carbon-sulfur bond, facilitated by a palladium catalyst generated from Pd(OAc)(2) and diphosphine ligand dpppe. The versatility of this approach is demonstrated by the synthesis of 30 representative allylic amines with excellent regio- and stereoselectivity. Mechanistic studies reveal that the Z-selectivity of the reaction is attributed to the formation of a palladacycle intermediate via Pd-N chelation. The synthetic utility of this method is further showcased by its successful gram-scale synthesis and subsequent transformations to diverse compounds.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Xiaoyun Wu, Wei Ma, Weijun Tang, Dong Xue, Jianliang Xiao, Chao Wang
Summary: A Fe-catalyzed amidation of allylic alcohols with chiral tert-butylsulfinamide has been developed for the synthesis of chiral sulfinamide olefin derivatives. The reaction proceeds under mild conditions with water as the only by-product.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Guangkuo Zeng, Lingyun Shen, Qingshu Zheng, Tao Tu
Summary: In this study, a palladium-catalyzed dehydrogenation-coupling-aromatization protocol was developed to access ortho-substituted phenols from cyclohexanols with primary alcohols. The method demonstrated broad substrate scope and resulted in clean byproducts of water and hydrogen gas. The ortho-mono- and ortho-disubstitutions could be readily controlled by N-heterocyclic carbene (NHC) ligands and the amount of base.
Article
Chemistry, Organic
Yinan Ai, Hanlin Yang, Chunying Duan, Xingwei Li, Songjie Yu
Summary: A new Co-catalyzed sequential C-C and C-F activation of gem-difluorinated cyclopropanes has been developed, allowing the formation of nucleophilic fluoroallylcobalt, followed by addition to aldehydes to yield linear (Z)- and (E)-fluorinated homoallylic alcohols. This discovery established a new strategy for the efficient transformation of gem-difluorinated cyclopropanes and synthesis of challenging fluorinated homoallylic alcohols.
Article
Chemistry, Organic
Renren Li, Haocheng Zhang, Bangkui Yu, Hanmin Huang
Summary: A novel palladium-catalyzed cascade annulative aminomethylamination of diene-tethered enynes with aminals is reported. This method allows for the efficient synthesis of functionalized benzofulvenes with excellent chemo- and regioselectivities, as well as high atom economy. Mechanistic studies reveal the preferential reaction of alkylpalladium species with 1,3-enyne over 1,3-diene in initiating the cyclizative aminomethylamination.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Guanlin Li, Ling Zhao, Yicong Luo, Youbin Peng, Kai Xu, Xiaohong Huo, Wanbin Zhang
Summary: Asymmetric desymmetrization is a powerful strategy for building stereocenters in asymmetric synthesis. This study reports a Pd/Cu catalyzed asymmetric desymmetrization reaction using a simple geminal dicarboxylate, which achieved good yields and high selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Bing-ru Shao, Wen-feng Jiang, Chao Zheng, Lei Shi
Summary: The precise synthesis of axially chiral molecules is highly valuable in pharmaceutics, fine chemicals, and materials science. However, the enantioselective synthesis of non-atropisomeric axially chiral alkylidene cycloalkanes has been a great challenge due to the remote distance between chirality-related groups or atoms. We developed a general efficient methodology using palladium-catalyzed asymmetric allylic alkylation, which showed excellent enantioselectivities, high yields, and a wide substrate scope. The additive effect played a crucial role in improving the chem- and enantioselectivity of this reaction. Due to the value and structural diversity of the products, this method provides an opportunity for further exploration of the applied potential of axially chiral olefins in related research fields.
Article
Chemistry, Organic
Rodney A. Fernandes, Ashvin J. Gangani, Arpita Panja
Summary: An efficient method using Pd-catalyzed reactions has been developed for the synthesis of 5-vinyl-2-isoxazolines, which can be further elaborated into various value-added products.
Article
Chemistry, Organic
Rodney A. Fernandes, Naveen Chandra, Ashvin J. Gangani, Gulenur N. Khatun
Summary: An efficient method for the synthesis of (E)-(3-alkoxybut-1-enyl)benzenes has been developed via Pd-catalyzed regioselective intermolecular hydroalkoxylation of 1-arylbutadienes. This method offers a simple operation, without the need for dry reaction conditions, and shows good tolerance to various substrates. The presence of chloromethyl methyl ether (MOMCl) as an additive is crucial to the success of the reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Jessica Margalef, Joseph S. M. Samec
Summary: This review evaluates the synthesis of alpha-sulfenylated carbonyl compounds based on green chemistry metrics, focusing on traditional routes as well as more recently developed methodologies. The assessment includes factors such as atom economy, E factor, safety, toxicity, and synthetic utility. The aim is to inspire researchers to apply green assessments to other methodologies and enhance the sustainability of their transformations.
Article
Biochemistry & Molecular Biology
Alexander Orebom, Davide Di Francesco, Patrick Shakari, Joseph S. M. Samec, Clara Pierrou
Summary: The study successfully prepared lignin esters by modifying lignin with fatty acids, and incorporated them into different thermoplastic polymers to improve dispersibility while maintaining tensile properties. The results demonstrate significant impacts of lignin esters on the thermal and mechanical behavior of the blends.
Article
Chemistry, Multidisciplinary
Elena Subbotina, Thanya Rukkijakan, M. Dolores Marquez-Medina, Xiaowen Yu, Mats Johnsson, Joseph S. M. Samec
Summary: In summary, lignin is a significant source of renewable aromatics, with potential for increased yields by selectively cleaving C-C bonds through oxidation reactions. This advancement is crucial for enhancing the sustainability and competitiveness of biorefining processes.
Article
Chemistry, Multidisciplinary
Suthawan Muangmeesri, Ning Li, Dimitrios Georgouvelas, Pierre Ouagne, Vincent Placet, Aji P. Mathew, Joseph S. M. Samec
Summary: The study showed a method to convert hemp hurd into high-content monophenolic compounds through RCF technology, resulting in dissolving-grade pulp and nanocellulose suitable for textile fiber production. This method may increase textile fiber production and obtain bio-oil for green chemicals.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Davide Di Francesco, Davide Rigo, Kiran Reddy Baddigam, Aji P. Mathew, Niklas Hedin, Maurizio Selva, Joseph S. M. Samec
Summary: In this study, a two-step procedure was developed to produce a thermoset material from sustainable sub-components. The cross-linking between KL lignin and AdA was activated using an acetylating agent, resulting in the formation of a cross-linking mixture. The esterification reactions were confirmed by spectroscopy, and the material transformed into a thermoset through heating.
Article
Chemistry, Analytical
Daniel Papp, Thanya Rukkijakan, Daria Lebedeva, Tommy Nylander, Margareta Sandahl, Joseph S. M. Samec, Charlotta Turner
Summary: The increased interest in using lignin as a feedstock to produce aromatic compounds requires advanced chemical analysis methods for lignin characterization. This study presents a novel method for quantifying lignin dimers using supercritical fluid chromatography with charged aerosol detection. The method was validated using synthesized lignin dimers and found to be effective for quantification. The study also emphasizes the importance of chromatographic peak resolution and introduces a digital peak sharpening technique to address it.
ANALYTICAL CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Maxim Galkin, Joseph S. M. Samec
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Martin Lawoko, Joseph S. M. Samec
Summary: Kraft pulping, a century-old process, has only recently seen commercial implementation of kraft lignin recovery in the past ten years. Lignin, as a by-product, is considered a sustainable material with immense potential, sparking significant research and development efforts to utilize kraft lignin. This article provides an overview of the current state of the field, highlighting recent examples of manipulating kraft lignin into thermoset materials or depolymerizing it for biofuels.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2023)
Article
Chemistry, Physical
Daria Lebedeva, Joseph S. M. Samec
Summary: Valorizing industrial side-streams is essential for sustainable biorefining. This study converted hemicellulose from kraft pulping into furfural with a 19% yield and further processed furfural into pentane and higher hydrocarbons with a 60% yield. The combination of Pd/C and ZSM-5 catalysts achieved full hydrodeoxygenation, generating aromatic or aliphatic compounds depending on reaction conditions. Using pentane as a carrier liquid enables a 100% renewable hydrocarbon stream.
SUSTAINABLE ENERGY & FUELS
(2023)
Article
Chemistry, Physical
Maria-Ximena Ruiz-Caldas, Varvara Apostolopoulou-Kalkavoura, Anna-Karin Hellstroem, Jutta Hildenbrand, Mikael Larsson, Aleksander Jaworski, Joseph S. M. Samec, Panu Lahtinen, Tekla Tammelin, Aji P. Mathew
Summary: We propose a new method for extracting cellulose nanocrystals (CNCs) from post-consumer cotton textiles by surface functionalization and mechanical treatment. The process involves esterification of cotton textiles using citric acid, followed by fibrillation in a microfluidizer. The resulting citrated cellulose nanocrystals (CitCNCs) exhibit higher yields and a higher surface group content compared to CNCs extracted through H2SO4 hydrolysis, although they have a broader size distribution and decreased thermal stability.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Analytical
Daniel Papp, Thanya Rukkijakan, Daria Lebedeva, Tommy Nylander, Margareta Sandahl, Joseph S. M. Samec, Charlotta Turner
Summary: A novel method for universal quantification of lignin dimers based on supercritical fluid chromatography with charged aerosol detection (CAD) was developed and applied to quantify lignin dimers in an oil obtained by reductive catalytic fractionation (RCF) of birch sawdust. The applicability of linear regression and quadratic calibration curves for quantification was evaluated and found to be equally appropriate. The response factors of lignin dimers were compared and showed little variation, enabling the use of a single calibrant for these compounds. The importance of chromatographic peak resolution in CAD was stressed and addressed using a digital peak sharpening technique.
ANALYTICAL CHEMISTRY
(2023)
Article
Agriculture, Multidisciplinary
Daria Lebedeva, Samuel Hijmans, Aji P. Mathew, Elena Subbotina, Joseph S. M. Samec
Summary: This study systematically investigated lignin from coconut coir pith and explored its potential for renewable utilization, achieving positive results through two different valorization approaches.
ACS AGRICULTURAL SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Davide Di Francesco, Kiran Reddy Baddigam, Suthawan Muangmeesri, Joseph S. M. Samec
Summary: The paper describes the process of organosolv pulping performed in a high-pressure Soxhlet extractor using carbon dioxide as a mild and recyclable acid. The system achieved a high yield of dissolving grade quality pulp from Populus trichocarpa and enabled reductive catalytic fractionation to obtain a lipophilic lignin oil without affecting the pulp's performance or purity.
Review
Chemistry, Multidisciplinary
Mahdi M. Abu-Omar, Katalin Barta, Gregg T. Beckham, Jeremy S. Luterbacher, John Ralph, Roberto Rinaldi, Yuriy Roman-Leshkov, Joseph S. M. Samec, Bert F. Sels, Feng Wang
Summary: The valorisation of lignin is crucial for the economic viability of the lignocellulosic biorefining industry. The lignin-first biorefining approach, which considers lignin valorisation in the design phase, has been shown to make the fullest use of lignocellulose. Despite the diverse approaches to reporting and analyzing results from lignin-first methods, we propose guidelines for analyzing critical data in order to facilitate direct comparisons between studies.
ENERGY & ENVIRONMENTAL SCIENCE
(2021)
