Article
Chemistry, Inorganic & Nuclear
Anand Pariyar, Debesh Sharma, Sagarmani Rasaily, Shivanand Chettri, Disha Sureka, Sudarsan Tamang
Summary: This study reports the synthesis of a novel 2D metal-organic framework with pre-existing unsaturated Lewis acid sites, which can be directly used for catalyzing organic transformations and synthesizing biologically active chiral imidazolidines. The material exhibits excellent reusability and high stereoselectivity.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Hyun Ji Jeon, Su Min Park, Yu Lim Lee, Sang-gi Lee
Summary: The palladium-catalyzed divergent asymmetric synthesis of chiral spiro-furanindoline derivatives is described. The zwitterionic alkoxy pi-allyl Pd(II) intermediate, generated catalytically from vinyl ethylene carbonate (VEC), could undergo ligand-controlled enantio-and diastereoselective dipolar [3 + 2] spiroannulation with indole-based azadienes to afford the optically active spiro-furanindolines embedding an all-carbon quaternary stereocenter in high yields (up to 99%) with good to excellent stereoselectivities (up to 99% ee and up to >94:6 dr).
Article
Chemistry, Applied
Jing Huang, Bo Jiang, Xiyuan Zhang, Yanfeng Gao, Xiufang Xu, Zhiwei Miao
Summary: A synthetic strategy for accessing functionalized azabicyclo[3.3.1]alkenones with three tertiary stereocenters has been developed. The method is scalable and the products can be transformed to various eight-membered-ring bridged heterocyclic molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Maniyamma Aswathy, Mohammed N. K. Sadik, Purushothaman C. Harikrishnan, Sasikumar Parameswaran, Kokkuvayil Vasu Radhakrishnan, Ravi S. Lankalapalli
Summary: This paper describes a method for stereoselective glycosylation using a chiral Bronsted acid, the (+)-isomenthol ester of pentacarbomethoxycyclopentadiene, with n-pentenyl glycosides in the presence of N-iodosuccinimide as the promoter, which offers a chiral recognition of racemic substrates.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Skyler D. Mendoza, Michael Rombola, Yujia Tao, Stephan J. Zuend, Roland Goetz, Martin J. McLaughlin, Sarah E. Reisman
Summary: An enantioselective Diels-Alder reaction using yttrium triflate as catalyst has been developed for the synthesis of chiral oxidized cyclohexenes. This method allows the preparation of a key intermediate in the synthesis of commercial herbicide cinmethylin.
Article
Chemistry, Physical
Hideyuki Ishihara, Jianhao Huang, Takuya Mochizuki, Manabu Hatano, Kazuaki Ishihara
Summary: A highly enantio- and diastereoselective carbonyl-ene cyclization was developed using chiral Lewis acid-assisted chiral Bronsted acid (LBA) catalysts, demonstrating high selectivity in both standard and tandem reactions. Mechanistic examinations propose a stepwise reaction pathway involving tertiary carbocation intermediates.
Article
Chemistry, Organic
Cong-Yun Tang, Jie Wu, Feng-Ting Ji, Fang Tian, Lin Peng, Liang-Liang Wang
Summary: Enantioenriched tricyclic tetrahydropyran derivatives were successfully synthesized through chiral phosphoric acid catalyzed intramolecular reactions, with good yields and excellent stereocontrol. The high enantioselectivity is attributed to the rationally designed remote dual hydrogen bonding interaction, which effectively arranges the conformation of the flexible substrate.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Freya M. M. Harvey, Alexandra H. H. Heidecker, Christian Merten, Thorsten Bach
Summary: Allenes with different substituents at their terminal carbon atom exhibit axial chirality and can be obtained in enantiopure form through a photochemical deracemization protocol. This study investigates the conditions under which allenoic acid derivatives undergo a Diels-Alder reaction with 1,3-cyclopentadienes and the resulting products. Cyclic derivatives (lactams, lactones) exhibited an exo-selective reaction catalyzed by the Lewis acid Eu(fod)(3), while acyclic derivatives mainly produced endo-products (with EtAlCl2 as the preferred Lewis acid). The exocyclic double bond exhibited excellent diastereoselectivity and achieved near-perfect chirality transfer. The method was successfully applied to the synthesis of sesquiterpenes beta-santalol (1) and 10(E)-beta-santalic acid (13).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Alice Pommainville, Dominic Campeau, Fabien Gagosz
Summary: (3+2) cycloaddition reactions are important and versatile synthetic tools in heterocyclic chemistry. The scope of these reactions can be expanded by using neutral three-atom components, resulting in various outcomes depending on structure and conditions. A new intramolecular (3+2) cycloaddition reaction was reported, which provides access to highly substituted fused thiophenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Christoph Wallach, Felix S. Geitner, Thomas F. Fassler
Summary: Despite being known for two decades, homoatomic nine-atom germanium clusters have been rarely investigated for their chemical properties. This study shows that Zintl ion main group-element clusters have a reactive lone pair of electrons, and introduces a new pathway for binding ligands to the [Ge-9] cluster core through Ge-C bond formation. The reactivity of [Ge-9{Si(TMS)(3)}(2)](2-) towards a series of Lewis acidic bromo-boranes is explored, leading to the formation of different products depending on reaction conditions. Overall, the study highlights the unique substitution patterns and reactivity of these germanium clusters in interaction with borane compounds.
Article
Chemistry, Organic
Katarina Stefkova, Michael G. Guerzoni, Yara van Ingen, Emma Richards, Rebecca L. Melen
Summary: Here, a mild, transition-metal-free, highly diastereoselective Lewis acid catalyzed methodology for the synthesis of isoxazolidine-based diazo compounds from the reaction between vinyldiazo esters and nitrones is reported. Interestingly, the diastereoselectivity of the isoxazolidine products is found to be contrasting to previous metal-catalyzed reactions. Furthermore, the same catalyst can be used with enol diazo esters, leading to the formation of Mukaiyama-Mannich products. These diazo products can be further functionalized to generate benzo[b]azepine and pyrrolidinone derivatives.
Article
Chemistry, Organic
Yaoyu Liang, Hongtai Huang, Nan Huang, Lihao Liao, Xiaodan Zhao
Summary: An efficient method for the synthesis of enantioenriched ?,?-azido nitriles through chiral sulfide-catalyzed asymmetric electrophilic thioazidation of allylic nitriles is reported. A wide range of substituents, both electron-deficient and -rich aryl, heterocyclic aryl, and alkyl groups, are suitable for the allylic nitrile substrates. The regio-, enantio-, and diastereo-selectivities of the reactions are excellent. The resulting chiral ?,?-azido nitriles can be easily converted into high-value-added chiral molecules that are not readily accessible by other methods, making them versatile platform molecules. Control experiments demonstrate the importance of the allylic nitrile group in controlling the reactivity and enantioselectivity of the reaction, leading to a broad substrate scope.
Article
Chemistry, Organic
Hai-Xia Wang, Mi-Mi Zhang, Ming-Sheng Xie, Hai-Ming Guo
Summary: Chiral isoxazole and carbocyclic pyrimidine nucleoside analogues were synthesized via cycloadditions, with high yields and enantiomeric excess, while avoiding racemization.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ludovic Leleu, Thomas Martzel, Arona Fall, Morgane Sanselme, Vincent Levacher, Sylvain Oudeyer, Jean-Francois Briere
Summary: By utilizing metal- and catalyst-free electrochemical conditions in an undivided cell, a series of easily available redox-active N-(acyloxy)phthalimide esters were reacted with chiral C5-substituted azomethine imines, resulting in an efficient and highly stereoselective addition reaction to produce an array of polyaminated hydrazine derivatives.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Shuichi Nakamura, Natsuki Matsumoto, Masato Kibe, Kazuki Abe, Tsunayoshi Takehara, Takeyuki Suzuki
Summary: This study reports the enantiodivergent reaction of ketimines derived from alpha-ketoesters with malononitriles using a single chiral source, resulting in the synthesis of various optically active compounds from the obtained malononitrile-derived alpha-amino acids. A proposed reaction mechanism explains the observed enantiodivergency in high yields with high enantioselectivities.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
M. A. Jalil Miah, Mukund P. Sibi, S. Chattopadhyay, Oluwole B. Familoni, Victor Snieckus
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Arvin Z. Yu, Eric M. Serum, Anna C. Renner, Jonas M. Sahouani, Mukund P. Sibi, Dean C. Webster
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2018)
Article
Chemistry, Multidisciplinary
Eric M. Serum, Catherine A. Sutton, Anna C. Renner, Dyuti Dawn, Mukund P. Sibi
PURE AND APPLIED CHEMISTRY
(2019)
Article
Chemistry, Multidisciplinary
Sukanya Nad, Mukund P. Sibi
HELVETICA CHIMICA ACTA
(2019)
Article
Chemistry, Multidisciplinary
Samantha D. Silbert, Eric M. Serum, John LaScala, Mukund P. Sibi, Dean C. Webster
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2019)
Article
Biochemistry & Molecular Biology
Shokoofeh Ghasemi, Mukund P. Sibi, Chad A. Ulven, Dean C. Webster, Ghasideh Pourhashem
Article
Chemistry, Multidisciplinary
Benjamin Poelloth, Mukund P. Sibi, Hendrik Zipse
Summary: The factors responsible for the kinetic resolution of alcohols by chiral pyridine derivatives have been elucidated through accurate competitive linear regression analysis. Increasing the size of the aromatic side chain accelerates the reaction rate of the major enantiomer, leading to the design of a new catalyst with increased steric bulk for higher enantioselectivity values. Experimental and theoretical results suggest that the enhancement of enantioselectivity is achieved by accelerating the transformation of the major enantiomer through attractive non-covalent interactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Catherine A. Sutton, Alexander Polykarpov, Keimpe Jan van den Berg, Alexander Yahkind, Linda J. Lea, Dean C. Webster, Mukund P. Sibi
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2020)
Review
Chemistry, Organic
Marcus Muresan, Hariharaputhiran Subramanian, Mukund P. Sibi, James R. Green
Summary: This minireview discusses the increasing importance of propargyl radicals as synthetic intermediates in recent years. It covers the mechanisms of their generation and reactions, as well as their applications in the synthesis of target molecules.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yehor Polunin, Timothy J. Burns, Eric M. Serum, Mukund P. Sibi, Andriy Voronov
Summary: Renewable 3-allyl-5-vinylveratrole (AVV) is a biobased cross-linkable vinyl monomer that can be synthesized from vanillin and potentially serve as a sustainable alternative to styrene in free-radical polymerization. By copolymerizing AVV with other monomers, materials with different viscoelastic behaviors can be obtained, offering a promising platform for controlling properties of biobased latex polymer networks.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Review
Chemistry, Multidisciplinary
Shovan Mondal, Frederic Dumur, Didier Gigmes, Mukund P. Sibi, Michele P. Bertrand, Malek Nechab
Summary: Benefiting from the increase in fundamental knowledge, there has been a continuous burst of new ideas and catalytic methods for enantioselective radical reactions in the past 20 years. This review provides a comprehensive survey of the progress achieved during this period, focusing on chiral organocatalysts and transition-metal redox catalysis. The review also discusses the merger of photocatalysis with organo- or metalla-photocatalysis and enzyme-catalyzed reactions involving radical intermediates.
Article
Chemistry, Multidisciplinary
Jingbo Wu, Yiqiu Qian, Catherine A. Sutton, John J. La Scala, Dean C. Webster, Mukund P. Sibi
Summary: A series of photocurable di(meth)acrylates based on furan-based diols were synthesized and evaluated for use in UV-curable coatings. These compounds exhibited high hardness, elastic modulus, and glass transition temperature, showing potential for applications in coating materials.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Review
Chemistry, Organic
Hariharaputhiran Subramanian, Mukund P. Sibi
Summary: Hydrogen atom transfer (HAT) is an important class of radical reactions. Despite extensive research, controlling the stereoselectivity of the HAT process remains challenging. This review highlights the use of small molecule chiral HAT reagents and catalysts to achieve stereoselectivity in free radical reactions, as well as the recent advancements in photoenzymatic catalysis for efficient HAT reactions.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Pharmacology & Pharmacy
Ali Divan, Mukund P. Sibi, Alexei Tulin
PHARMACOLOGY RESEARCH & PERSPECTIVES
(2020)
Article
Chemistry, Organic
Quinlyn T. Waulters, Waidath Bio-Sawe, Russell Hofmann, Mukund P. Sibi
