Article
Chemistry, Physical
Aleksandra Buchcic-Szychowska, Anna Zawisza, Stanislaw Lesniak, Michal Rachwalski
Summary: In this study, chiral aziridine-phosphines were used as catalysts in the asymmetric Morita-Baylis-Hillman reaction. The desired chiral products were obtained in moderate to high yields and with a high enantiomeric excess. The use of enantiomeric pairs of catalysts led to the formation of products with opposite absolute configurations.
Review
Chemistry, Physical
Hugo Santos, Lucas A. Zeoly, Manoel T. Rodrigues Jr, Fabio S. Fernandes, Ralph C. Gomes, Wanda P. Almeida, Fernando Coelho
Summary: Since its discovery in the late 1960s, the Morita-Baylis-Hillman (MBH) reaction has been a powerful carbon-carbon sigma-bond-forming reaction, producing small polyfunctionalized molecules. Advances in functional catalysts and reaction conditions have been made to improve the reaction rate, substrate scope, and enantioselectivity. This review provides an updated summary of the main improvements in catalytic systems for the MBH reaction over the past decade until nowadays, aiming to inspire further investigations and overcome the remaining challenges of this fascinating transformation.
Article
Chemistry, Organic
Naruhiro Gondo, Koki Fujimura, Ryuichi Hyakutake, Yoshihiro Ueda, Takeo Kawabata
Summary: Asymmetric regioselective vinylogous aza-Morita-Baylis-Hillman reactions were conducted using organocatalysis. The reactions between 3-vinylcyclopentenone and various aldimines, in the presence of chiral pyrrolidinopyridine catalysts, yielded 7-adducts with high regioselectivity and moderate enantioselectivity.
TETRAHEDRON LETTERS
(2023)
Article
Parasitology
Ana Carolina Santana Vieira, Mariana da Silva Santos, Anderson Brandao Leite, Amanda Evelyn da Silva, Luiz Henrique Agra Cavalcante-Silva, Gabrielle de Souza Augusto Pereira, Sany Delany Gomes Marques, Barbara Viviana de Oliveira Santos, Alysson Wagner Fernandes Duarte, Aline Cavalcante de Queiroz, Kristerson Reinaldo de Luna-Freire, Magna Suzana Alexandre-Moreira
Summary: Leishmaniasis is a neglected disease with limited treatment options and adverse effects. This study evaluated the antileishmanial activity of several derivatives and found that one derivative (1G) showed activity against both promastigote and amastigote forms with low toxicity to macrophages.
PARASITOLOGY RESEARCH
(2022)
Article
Chemistry, Physical
Yinuo Li, Cuiyu Bao, Zhoutong Sun, Wuyuan Zhang, Bo Yuan
Summary: The oxidation of benzylic alcohols coupled with the Morita-Baylis-Hillman (MBH) reactions in biocatalytic compatible conditions was evaluated. One-pot cascades were described and compared, including a chemoenzymatic cascade with galactose oxidase (GOase M3-5) and 1,4-Diazabicyclo [2.2.2] octane (DABCO), a concurrent dual-enzyme cascade with GOase M3-5 and a computationally designed enzyme MBHase (BH32.14), and a whole cell biotransformation with co-expression modules of the two enzymes. The cascades showed high conversions and yields, with some products having high optical purity.
Article
Chemistry, Multidisciplinary
Harshitha N. Anchan, Saikat Dutta
Summary: In this study, the MBH reaction of biomass-derived 5-substituted-2-furaldehydes and acrylates was systematically investigated, and several novel MBH adducts were synthesized. The reactions were performed under solvent-free conditions using 1,4-diazabicyclo[2.2.2]octane (DABCO) as the organocatalyst, resulting in the production of spectroscopically pure products with good to excellent yields. DABCO was also successfully recovered and recycled.
Article
Chemistry, Organic
Nilton S. Camilo, Hugo Santos, Lucas A. Zeoly, Fabio S. Fernandes, Manoel T. Rodrigues Jr, Thiago S. Silva, Samia R. Lima, Jose Claudio Serafim, Aline S. B. de Oliveira, Arthur G. Carpanez, Giovanni W. Amarante, Fernando Coelho
Summary: The Morita-Baylis-Hillman (MBH) reaction is an important C-C bond-forming transformation, but the slow reaction rate with electron-rich electrophilic partners limits its widespread use. By introducing Bronsted acids, the rate of DABCO-catalyzed MBH reactions can be increased, and this method is simple, compatible with a wide range of reagents.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Victoria Dimakos, Daniel P. Canterbury, Sebastien Monfette, Philipp C. Roosen, Stephen G. Newman
Summary: This study describes a Pd-catalyzed method for the direct and selective alpha-arylation of cyclic enones using (hetero)aryl triflates. Optimized ligands and additives were employed to achieve high selectivity. Preliminary mechanistic investigations suggest that the reaction proceeds through enone activation and Pd-catalyzed enolate arylation, resembling a Morita-Baylis-Hillman reaction.
Article
Chemistry, Organic
Niannian Ni, Jiawei Chen, Siyu Ding, Dongping Cheng, Xiaonian Li, Xiaoliang Xu
Summary: The Ru-catalyzed coupling reaction of Morita-Baylis-Hillman (MBH) adducts with tertiary amines and alpha-trimethylsilyl amines under visible light showed different chemical reaction characteristics when compared to MBH adducts with ester groups as withdrawing-electron groups. The universality of substrates has been extended, allowing for the synthesis of structurally complementary acrylonitriles in satisfied yields under mild conditions and providing an opportunity to discover new meaningful bioactive compounds.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Lei Zhang, Wangzhen Bao, Yuchen Liang, Wenjing Pan, Dongyang Li, Lichun Kong, Zhi-Xiang Wang, Bo Peng
Summary: This study demonstrates the reversal of stereoselectivity in MBH-type [3,3]-rearrangement by using a new pair of rearrangement partners, leading to the synthesis of different types of alpha-aryl alpha,beta-unsaturated carbonyl derivatives. Mechanistic studies provide insights into the reaction pathway and the opposite stereoselectivities observed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Naruhiro Gondo, Ryuichi Hyakutake, Koki Fujimura, Yoshihiro Ueda, Katsuhiko Nakano, Ryosuke Tsutsumi, Masahiro Yamanaka, Takeo Kawabata
Summary: In this study, catalyst-controlled vinylogous aza-MBH reactions of vinylcyclopentenone were conducted, showing that DABCO-catalysis led to exclusive formation of alpha-adducts while DMAP-catalysis predominantly produced gamma-adducts. It was found that the rate-determining step for the DABCO-catalyzed reactions was the Mannich-type C-C bond forming step, while for the DMAP-catalyzed reactions, it appeared to be the beta-elimination step.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Prashant Shukla, Ambika Asati, Devkumari Patel, Manorama Singh, Vijai K. K. Rai, Ankita Rai
Summary: This study reports on the Morita Baylis-Hillman (MBH) reaction using various aldehydes with acrylonitrile and methyl acrylate as electron-deficient alkenes. A novel catalyst, EDC.HCl, is utilized in the presence of CuI to synthesize the MBH adduct. The synthetic protocol shows excellent product yield (up to 99%), ambient reaction conditions, shorter reaction time, and no side product formation.
Review
Biochemistry & Molecular Biology
Wanyama Peter Juma, Dubekile Nyoni, Dean Brady, Moira L. Bode
Summary: The Morita-Baylis-Hillman (MBH) reaction produces highly functionalized allylic alcohols with new stereogenic centers that can be transformed into various products, some of which have medicinal potential. While some asymmetric syntheses of MBH adducts have been reported, a universally applicable method is still needed. Biocatalytic methods for synthesis and enzymatic kinetic resolution of MBH adducts have been explored, with enzymes like lipases, esterases, and nitrile-converting enzymes showing promise in achieving high selectivity in most cases.
Article
Chemistry, Physical
Ricardo Lucas Gomes Pimentel, Rodolfo B. da Silva, Mario Luiz Araujo de Almeida Vasconcellos, Claudio Gabriel Lima-Junior, Fausthon F. da Silva
Summary: This study explores the synthesis and characterization of a mixed-metal copper-manganese iminodiacetate 1D coordination polymer (Cu/Mn-IDA) and its application as a catalyst for the Morita-Baylis-Hillman reaction. The results demonstrate that under optimized conditions, the catalyst can achieve yields of up to 87% for various aldehyde substrates. Additionally, the catalyst exhibits good recyclability.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Organic
Jianning Liao, Jipan Dong, Jiaqing Xu, Wei Wang, Yongjun Wu, Yuxia Hou, Hongchao Guo
Summary: A phosphine-catalyzed [3 + 2] annulation reaction has been developed in this study to synthesize multifunctional isoxazoles with moderate to good yields and diastereoselectivities. The use of a spirocyclic chiral phosphine catalyst resulted in up to 89% ee.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Marta Romaniszyn, Katarzyna Gronowska, Lukasz Albrecht
Summary: An organocatalytic 1,6-addition using 4-(alk-1-en-1-yl)-3-cyanocoumarins as acceptors has been developed, enabling the synthesis of hybrid molecules bearing two biologically relevant units with good site-selectivity and efficiency through appropriate substrate design and the application of a quinine-derived catalyst.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Biochemistry & Molecular Biology
Krzysztof Kaczmarek, Barbara Pacholczyk-Sienicka, Lukasz Albrecht, Janusz Zabrocki, Ronald J. Nachman
Summary: A facile solid-phase synthetic method for incorporating the imidazoline ring motif into bioactive peptides is reported. An imidazoline peptidomimetic analog of an insect pyrokinin neuropeptide was synthesized via a cyclization reaction of an iminium salt generated from the preceding amino acid and 2,4-diaminopropanoic acid (Dap).
Article
Biochemistry & Molecular Biology
Maciej Saktura, Anna Skrzynska, Sebastian Frankowski, Sylwia Wodka, Lukasz Albrecht
Summary: An organocatalytic 1,3-dipolar cycloaddition reaction between 2-nitrobenzofurans or 2-nitrobenzothiophene and N-2,2,2-trifluoroethyl-substituted isatin imines has been developed in this study. The stereochemical efficiency of the process was crucially dependent on the use of squaramide derivative in bifunctional organocatalysis. The utility of the obtained cycloadducts was confirmed in selected transformations, including the removal of nitro groups via both aromative and non-aromative pathways.
Article
Chemistry, Applied
Artur Przydacz, Aleksandra Topolska, Anna Skrzynska, Sebastian Frankowski, Lukasz Albrecht
Summary: This manuscript presents the application of amino isobenzofulvene intermediates as pentaenamines in a 1,6-addition reaction. The alkylation of the indene ring in indene-2-carbaldehydes with para-quinone methides was achieved, with the stereoselectivity controlled by C-2-symmetric 2,5-diphenylpyrrolidine. The developed process utilizes the reactivity of amino isobenzofulvene intermediates derived from indene-2-carbaldehydes in a non-cycloadditive manner.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Artur Przydacz, Aleksandra Topolska, Anna Skrzynska, Lukasz Albrecht
Summary: A dearomative formal (4+2)-cycloaddition reaction has been established using NHC-catalysis between 2-substituted 3-furaldehydes derivatives and isatins or alpha,alpha,alpha-trifluoroacetophenones. Highly reactive NHC-bound heterocyclic o-QDM intermediates derived from 3-furaldehydes play a key role in the process, leading to the formation of structurally diverse 6,7-dihydro-4H-furo[3,2-c]pyran-4-ones in moderate to high yields. The obtained (4+2)-cycloadducts also show potential in the synthesis of spirooxindole derivatives containing 6,7-dihydro-4H-furo[3,2-c]pyran scaffold.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Aleksandra Topolska, Sebastian Frankowski, Lukasz Albrecht
Summary: The application of differentiating catalysis in the [4 + 2]-cycloaddition reaction between 2-alkyl-3-formylheteroarenes and alpha,beta-unsaturated aldehydes is described in this paper. The use of the same aminocatalyst allows for independent activation of both starting materials, achieving high enantio- and diastereoselectivity through LUMO-lowering and HOMO-rising principles. The combination of dearomative dienamine activation with iminium ion chemistry further improves the outcome of the process.
Article
Chemistry, Organic
Marta Romaniszyn, Leslaw Sieron, Lukasz Albrecht
Summary: This study demonstrates the use of organocatalytic Brønsted base activation to generate 2π-components for the diastereoselective [8 + 2]-cycloaddition reaction involving 8,8-dicyanoheptafulvene. The use of dienolates leads to the formation of biologically relevant polycyclic products bearing a γ-butyrolactone structural motif, thus expanding the synthetic potential of Brønsted base activated higher-order cycloadditions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Marek Moczulski, Angelika Artelska, Lukasz Albrecht, Anna Albrecht
Summary: The photocatalytic decarboxylative alkylation of 3-cyanochromones using triphenylphosphine and potassium iodide as photoredox-mediators has been described. This method is cost-effective and interesting, and allows for obtaining a number of biologically relevant products.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Barbara Pacholczyk-Sienicka, Grzegorz Ciepielowski, Jakub Modranka, Tomasz Bartosik, Lukasz Albrecht
Summary: The targeted quantitative NMR (qNMR) approach is a powerful tool for classifying and determining the authenticity of honey samples. In this study, the chemical profiles of different types of Polish honey samples were determined using qNMR, and pattern recognition was performed using principal component analysis (PCA). The results showed that qNMR combined with chemometric analysis can be used as a supplementary tool for specifying honeys.
Article
Chemistry, Applied
Justyna Kowalska, Beata Lukasik, Sebastian Frankowski, Leslaw Sieron, Lukasz Albrecht
Summary: This paper demonstrates the application of organocatalysis in the synthesis of 2,3-dihydro-1H-pyrrolizines. The formal (3+2)-cycloaddition of alpha,beta-unsaturated aldehydes and pyrrole-based hydrazone was achieved through aminocatalytic iminium ion activation, resulting in products with high chemical yields and excellent stereocontrol. The developed method was also utilized in the first organocatalytic synthesis of the non-steroidal anti-inflammatory drug ketorolac.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Letter
Chemistry, Organic
Marta Romaniszyn, Anna Skrzynska, Joanna Dybowska, Lukasz Albrecht
Summary: A novel organocatalytic reaction cascade has been described for the stereocontrolled functionalization of cyanocoumarins, producing biologically active coumarin and delta-lactone-fused products.
Article
Chemistry, Multidisciplinary
Mateusz Dyguda, Anna Skrzynska, Leslaw Sieron, Lukasz Albrecht
Summary: This manuscript describes the first enantioselective dearomative Michael addition between alpha,beta-unsaturated aldehydes and 2-nitrobenzofurans realized under N-heterocyclic carbene activation. The reaction can efficiently form biologically important heterocycles with high yields and stereoselectivities.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Marek Moczulski, Ewelina Kowalska, Elzbieta Kusmierek, Lukasz Albrecht, Anna Albrecht
Summary: This study describes a doubly decarboxylative, photoredox synthesis method which successfully synthesized 4-substituted-chroman-2-ones and 2-substituted-chroman-4-ones. Key parameters include visible light, photoredox catalyst, base, anhydrous solvent, and inert atmosphere.
Article
Biochemistry & Molecular Biology
Barbara Pacholczyk-Sienicka, Grzegorz Ciepielowski, Lukasz Albrecht
Summary: Counterfeit goods are a major underground business globally, causing both financial losses to honest producers and potential health hazards to consumers. The perfume industry, especially in the realm of designer-inspired fragrances, is particularly susceptible to counterfeits, prompting the need for innovative authentication methods like H-1 NMR spectroscopy.
Article
Chemistry, Multidisciplinary
Beata Lukasik, Justyna Kowalska, Sebastian Frankowski, Lukasz Albrecht
Summary: A new umpolung approach has been developed for the asymmetric Friedel-Crafts-type alkylation of electron-poor heteroaromatic systems using hydrazones. The method shows excellent enantioselectivities under aminocatalytic conditions, and also provides a unique strategy for the asymmetric functionalization of electron-poor heteroaromatic systems.
CHEMICAL COMMUNICATIONS
(2021)