Article
Chemistry, Organic
Luigi Dolcini, Tommaso Gandini, Riccardo Castiglioni, Alberto Bossi, Marta Penconi, Alberto Dal Corso, Cesare Gennari, Luca Pignataro
Summary: This study investigates the use of organic photocatalysts for visible light-promoted beta-functionalization of carbonyl compounds. Donor-acceptor cyanoarenes showed the best results among the tested dyes, promoting the desired transformations in moderate to good yields. The reaction scope was explored on substrates with different steric and electronic properties, and a reductive quenching mechanism involving a transient 5 pi e(-) activation mode was proposed based on fluorescence quenching analysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
J. Daniel Bailey, Edward Helbling, Amey Mankar, Matthew Stirling, Fred Hicks, David K. Leahy
Summary: Reducing or eliminating organic solvent use in pharmaceutical manufacturing is a highly effective way to reduce environmental, health, and safety impacts. The process described utilizing primarily water-based methods significantly reduces material inputs and organic solvent use, while surprisingly using less water and improving overall yield compared to traditional methods.
Article
Chemistry, Organic
Xiaohan Li, Karthik S. Iyer, Ruchita R. Thakore, David K. Leahy, J. Daniel Bailey, Bruce H. Lipshutz
Summary: Highly valued products can be produced through reductive aminations using shelf-stable bisulfite addition compounds of aldehydes under aqueous micellar catalysis conditions. The readily available alpha-picolineborane serves as the stoichiometric hydride source, and recycling of the aqueous reaction medium is easily achieved. Several applications to targets in the pharmaceutical industry have been documented.
Article
Chemistry, Organic
Marina Briand, Linh D. Thai, Flavien Bourdreux, Nicolas Vanthuyne, Xavier Moreau, Emmanuel Magnier, Elsa Anselmi, Guillaume Dagousset
Summary: Site-selective trifluoromethylation of silyl dienol ethers derived from alpha,ss-unsaturated aldehydes, ketones, and amides was achieved for the first time in the remote gamma position. An unprecedented enantioselective C(sp(3))-H perfluoroalkylation process is disclosed.
Article
Chemistry, Organic
Vera A. Vil, Evgenii S. Gorlov, Bing Yu, Alexander O. Terent'ev
Summary: The oxidative C-O coupling of cyclic diacyl peroxides with acetals enables the selective functionalization of the non-activated acetal alpha-position. The reaction produces alpha-acyloxy acetals with a free carboxylic acid group in yields ranging from 42-85%.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Biochemistry & Molecular Biology
Tingting Wang, Changmeng Liu, Dong Xu, Jiaxi Xu, Zhanhui Yang
Summary: A highly chemoselective method for converting alpha, beta-disubstituted nitroalkenes to ketones has been developed using an acid-compatible iridium catalyst. Nitroalkenes can be readily converted to ketones at a certain ratio with high isolated yields. A new mechanistic mode has been proposed, and the pH value is found to play a crucial role in controlling the chemoselectivity.
Article
Chemistry, Multidisciplinary
Florian Puls, Philipp Linke, Olga Kataeva, Hans-Joachim Knoelker
Summary: This paper describes a convenient method for the oxidation of olefins to ketones using Fe(dbm)(3) or a combination of iron(II) chloride and neocuproine as catalysts and phenylsilane as an additive. The reactions are efficient and have a high yield and selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Igor T. Cunha, Huilin Yang, Philip G. Jessop
Summary: Biomass conversion to organic products is crucial for a sustainable society, but current energy costs and environmental impacts, particularly in removing water, remain problematic. The new method of high pressure switchable water (HPSW) shows promise in more efficiently separating organic products from water by changing the polarity of organic liquids and utilizing CO2 pressure.
Article
Chemistry, Organic
Zhi Zhang, Liansuo Zu
Summary: The study successfully synthesized a steroid-sterigmatocystin heterodimer using a concise method, including cascade dialdehyde cyclization, phenol-assisted reductive alkylation, and SNAr reaction. The research also explored a glycosylation-inspired method to provide the acetal linkage with ergosterol peroxide.
Article
Multidisciplinary Sciences
Mouxin Huang, Long Zhang, Tianrun Pan, Sanzhong Luo
Summary: This study presents a distinctive photochemical E/Z isomerization strategy for the deracemization of α-branched aldehydes, which involves the use of simple aminocatalysts and readily available photosensitizers. The method enables the direct transformation of racemic α-branched aldehydes into enantiopure α-tertiary carbonyls with high selectivity.
Article
Chemistry, Applied
Nagarajan Ramkumar, Arturs Sperga, Sergey Belyakov, Anatoly Mishnev, Dzintars Zacs, Janis Veliks
Summary: Fluoroalkyl ethers have been extensively researched in the fields of pharmaceutical, agrochemical, nuclear imaging, and material sciences, leading to the development of new synthetic methods. Radical fluoroalkoxylation has emerged as a promising approach for synthesizing fluoroalkyl ethers. This study introduced a solid, easily accessible redox-active N-O reagent, 1-(fluoromethoxy)-3-methyl-benzotriazolium triflate (FMBT), which acts as a radical source of (mono)fluoromethoxy group under photocatalytic conditions. The synthetic potential of FMBT was demonstrated in the functionalization of olefins to obtain amino and ketomonofluoromethyl ethers, contributing to the study of chemical biology and drug discovery.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Nora Almutairi, Srikanth Vijjamarri, Guodong Du
Summary: Manganese (III) complexes supported by salan ligands were synthesized and examined as catalysts in the hydrosilylation of carbonyl compounds. Manganese (III) chloride complexes exhibited minimal catalytic efficacy without activation of silver perchlorate, while manganese (III) azide complexes showed good activity in this reaction. Under optimized conditions, various aldehydes and ketones could be reduced with high yields and tolerance to different functional groups. The possible mechanisms of silane activation and hydrosilylation were discussed based on experimental observations.
Article
Chemistry, Organic
Xiao-Guang Yang, Jun-Jie Li, Feng-Huan Du, Yu-Xin Cheng, Chi Zhang
Summary: In this study, a method for dehydroxytrifluoromethylthiolation of alcohols using a combination of hypervalent iodine(III) reagent TFTI and N-heterocyclic carbenes is reported. This method exhibits excellent stereospecificity and chemoselectivity, resulting in clean inversion of the configuration of hydroxyl groups. It can also be utilized for late-stage modification of structurally complex alcohols.
Article
Chemistry, Organic
Yaseen Hussain, Deepak Sharma, Pankaj Chauhan
Summary: An unprecedented highly stereoselective synthesis of pyrrolo[1,2-d][1,4]oxazepin-3(2H)-ones has been achieved through photoredox/N-heterocyclic carbene (NHC) relay catalysis. Substituted dibenzoxazepines and aryl/heteroaryl enals were successfully converted to dibenzoxazepine-fused pyrrolidinones with excellent diastereo- and enantioselectivities via amine oxidation and [3 + 2] annulation reactions catalyzed by organic photoredox catalysis and NHC, respectively.
Article
Chemistry, Organic
Yaseen Hussain, Deepak Sharma, Tamanna, Pankaj Chauhan
Summary: A novel and highly selective synthesis of pyrrolo[1,2-d][1,4]oxazepin-3(2H)-ones has been achieved using photoredox/N-heterocyclic carbene (NHC) relay catalysis. Various substituted dibenzoxazepines and aryl/hetereoaryl enals were efficiently converted to imines through the organic photoredox catalysis-promoted amine oxidation, followed by a NHC-catalyzed [3 + 2] annulation reaction to afford dibenzoxazepine-fused pyrrolidinones with excellent diastereo- and enantioselectivities.
Article
Chemistry, Organic
Carolina Mendez-Galvez, Matthias Bohme, Reko Leino, Risto Savela
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Risto Savela, Dieter Vogt, Reko Leino
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Review
Chemistry, Multidisciplinary
Asiri A. Hettikankanamalage, Robert Lassfolk, Filip S. Ekholm, Reko Leino, David Crich
Article
Biochemistry & Molecular Biology
Miralda Madar Johansson, Eva Belurier, Anastassios C. Papageorgiou, Anders P. Sundin, Jani Rahkila, Teemu Kallonen, Ulf J. Nilsson, Santeri Maatsola, Thomas K. M. Nyholm, Jarmo Kapyla, Jukka Corander, Reko Leino, Jukka Finne, Susann Teneberg, Sauli Haataja
JOURNAL OF BIOLOGICAL CHEMISTRY
(2020)
Article
Biochemistry & Molecular Biology
Robert Lassfolk, Sara Bertuzzi, Ana Arda, Johan Warna, Jesus Jimenez-Barbero, Reko Leino
Summary: The phenomenon of acyl group migration in carbohydrates was studied in a trisaccharide model compound and shown to potentially occur in native polysaccharides as well. The implications of this migration process on cell signaling events and plant growth are intriguing areas for further research.
Article
Chemistry, Multidisciplinary
Robert Lassfolk, Manuel Pedron, Tomas Tejero, Pedro Merino, Johan Warna, Reko Leino
Summary: Acyl group migration plays a significant role in the synthesis, isolation, manipulation and purification of acylated organic compounds containing free hydroxyl groups, especially carbohydrates. Our study reveals that the anomeric configuration in monosaccharides, along with the relative configurations of other hydroxyl groups and the properties of the migrating acyl group, greatly influence the migration rate.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Ida Mattsson, Manu Lahtinen, Ruzal Sitdikov, Bianca Wank, Tiina Saloranta-Simell, Reko Leino
Summary: In the last decades, the synthesis and design of low molecular weight organogelators has gained increasing attention. In this work, three potential gelators have been prepared from allylated D-mannose and thoroughly characterized. The results showed that two of the compounds selectively formed gels with hydrocarbon solvents. The most promising gelator compound has the possibility for customizing the gelation properties by further chemical modification or utilizing the alkene group as a linker to increase the mechanical strength of the gel.
CARBOHYDRATE RESEARCH
(2022)
Article
Chemistry, Physical
Gabriele Beltrame, Ida Mattsson, Pia Damlin, Zenghua Han, Carita Kvarnstrom, Reko Leino, Baoru Yang
Summary: This study utilized solid state 13C NMR and FTIR spectroscopy to non-invasively investigate the sterile conk caused by the infection of Inonotus obliquus. The results showed clear distinction between the outer and inner layers of the sterile conk and similarity to wood tissues. The multivariate data analysis also revealed similarity between the sterile conk inner layers and decayed wood and hyphae of I. obliquus, suggesting the need for further studies to revise and clarify the classification of I. obliquus.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Organic
Robert Lassfolk, Manuel Pedron, Tomas Tejero, Pedro Merino, Johan Warna, Reko Leino
Summary: Acetyl groups in oligosaccharides can migrate within one saccharide unit and between different saccharide units. Xyloglucans and xylans are common naturally acetylated polysaccharides in nature, playing important roles in plant cells. Understanding the migration of acetyl groups can help understand the biological activity of polysaccharides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Robert Lassfolk, Reko Leino
Summary: Acyl group migration has been studied extensively due to its relevance to the synthesis, isolation, and purification of acyl-bearing compounds. It also plays a role in the metabolism of pharmaceuticals. Recent evidence suggests that acyl group migration may occur even over glycosidic bonds, potentially impacting the biological activity of natural polysaccharides in host cells. While previous studies have investigated migration in carbohydrates, comprehensive computational investigations supporting the proposed mechanisms are lacking.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Ida Mattsson, Johanna Majoinen, Manu Lahtinen, Thomas Sandberg, Anna Fogde, Tiina Saloranta-Simell, Orlando J. Rojas, Olli Ikkala, Reko Leino
Summary: Conformational rigidity plays a crucial role in the self-assembly and liquid crystallinity of block molecules. The stereochemistry of carbohydrate-based assemblies is an important parameter to be considered in material design.
Article
Chemistry, Inorganic & Nuclear
Veronika D. Badazhkova, Risto Savela, Reko Leino
Summary: Selective oxidation of lignin diol model compounds and lignin was achieved using a transfer hydrogenation methodology with a ruthenium catalyst. This method allows for the selective oxidation of benzylic secondary alcohols in model diols and spruce milled wood lignin using a commercially available Shvo catalyst under aerobic conditions. The yields of six ketoalcohols from the model compounds, including lignin monomers with 5-5' and beta-O-4 linkages, ranged from 70-92%. This developed method can be used as an intermediate step to introduce new functional groups into lignin-type structures and lignin for further modifications.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Robert Lassfolk, Atte Aho, Dmitry Yu Murzin, Reko Leino
Article
Chemistry, Multidisciplinary
Ida Mattsson, Ruzal Sitdikov, Andreas C. M. Gunell, Manu Lahtinen, Tiina Saloranta-Simell, Reko Leino
Article
Chemistry, Physical
Risto Savela, Nataliya D. Shcherban, Marko M. Melander, Igor Bezverkhyy, Irina L. Simakova, Otto Langvik, Ekaterina Kholkina, Tamara Schindler, Annabelle Krauss, Karoliina Honkala, Dmitry Yu Murzin, Reko Leino
Summary: Selective hydrogenation of unsaturated imines over heterogeneous catalysts, specifically with iridium on carbon nitrides and amphoteric metal oxides in toluene solvent, provides the best selectivity towards unsaturated amines. This study demonstrates a promising catalytic performance and chemoselectivity, which has not been reported before, under atmospheric hydrogen pressure and low temperatures.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)