Article
Chemistry, Applied
Jen-Yu Kuan, I-Ting Chen, Hsuan Lin, Jeng-Liang Han
Summary: We have developed a substrate-dependent, regio- and stereocontrolled diversity-oriented organocatalytic vinylogous Michael addition/cyclization cascade of 2-alkylidene indane-1,3-diones with enals, using secondary amines as the catalyst. This method allows for the selective synthesis of spiroindane-1,3-diones, tetrahydrofluoren-9-one derivatives, and benzofused oxabicyclo[3.3.1]nonanes. Plausible catalytic pathways have been proposed, and DFT calculations have clarified the mechanisms involved.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Irma Garcia-Monzon, Jorge Borges-Gonzalez, Tomas Martin
Summary: The heterogenization of homogeneous catalysts onto a solid support is a crucial step towards sustainable chemistry. In this study, we developed a series of polymer-supported tetrahydropyran-based hybrid dipeptides as active catalysts for the enantioselective Michael addition of aldehydes to beta-nitrostyrenes. The optimal anchor position and orientation between the catalyst and solid support, as well as the linker length, were carefully designed to enhance the catalytic efficiency. These supported catalysts exhibited high yields and enantiomeric excesses, and detailed deactivation studies provided important insights for prolonging their useful life.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Eugenia Marques-Lopez, Isaac G. Sonsona, Miryam Garces-Marin, M. Concepcion Gimeno, Raquel P. Herrera
Summary: In this study, the potential of phosphites as nucleophiles for the asymmetric synthesis of chiral chromene derivatives was explored. By employing asymmetric organocatalyzed phospha-Michael addition, chiral chromenylphosphonates were synthesized using a bifunctional squaramide. The optimized protocol provided good reactivity with yields of up to 95% and chiral products with an enantiomeric excess of up to 98%.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Biochemistry & Molecular Biology
Xiao-Yan Dong, Da-Ming Du
Summary: This paper investigated the organocatalytic asymmetric 1,4-Michael addition reaction of azadienes and alpha-thiocyanoindanones, successfully synthesizing a series of chiral thiocyano compounds. By describing a possible reaction mechanism, it broadens the scope of application of azadiene substrates.
Article
Chemistry, Multidisciplinary
Esteban Matador, Javier Iglesias-Siguenza, David Monge, Pedro Merino, Rosario Fernandez, Jose M. Lassaletta
Summary: A highly enantio- and diastereoselective thiourea-catalyzed dearomatization of isoquinolines has been developed using N-tert-butylhydrazones as key neutral reagents, leading to the formation of appealing dihydroisoquinoline derivatives with excellent stereocontrol. Experimental and computational data support the generation of highly ordered complexes that play a crucial role in the selective and high-yielding transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Abhisek Midya, Laxman Devidas Khalse, Prasanta Ghorai
Summary: In this study, an amine-catalyzed reductive aldol-condensation followed by an intramolecular reductive Michael-addition cascade was demonstrated, using Hantzsch ester as a hydride source to a keto-bis-enone, leading to the synthesis of enantio- and diastereoselective benzannulated diquinanes with three consecutive stereocenters, including an all-carbon quaternary formyl stereocenter. Interestingly, changing the tether from an aliphatic to an aromatic moiety resulted in a change in reactivity, where an asymmetric aldol reaction, followed by an iminium/enamine isomerization and diastereoselective Michael addition reaction, resulted in the formation of a bis-benzannulated diquinane with vicinal congested quaternary chiral centers.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Zaneta A. Mala, Mikolaj J. Janicki, Robert W. Gora, Krzysztof A. Konieczny, Rafal Kowalczyk
Summary: Dithiomalonates have been shown to be active nucleophiles in stereoselective additions, with Cinchona squaramides facilitating chirality transfer and mechanochemical approach proving to be effective.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Dong-Xing Zhu, Jian-Guo Liu, Ming-Hua Xu
Summary: A one-pot reaction has been developed for the stereodivergent synthesis of diverse 2,3-disubstituted dihydrobenzofurans under mild conditions with high yields and stereoselectivity. By appropriate permutations of two chiral catalysts, a wide range of chiral products can be accessed, demonstrating the ability of two chiral catalysts to independently control two contiguous stereogenic centers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Corinne Coutant, Paul De Bonfils, Pierrick Nun, Vincent Coeffard
Summary: The advent of asymmetric organocatalysis has revolutionized the way chemists create or break chemical bonds, enabling new strategies for enantioselective functionalization. This success is attributed to various activation modes and the availability of numerous chiral organic catalysts. Selective functionalization of compounds with multiple activation sites, such as cyclohexanone-derived dienones, has also contributed to breakthroughs in this field. These compounds can undergo diverse transformations and offer new opportunities for natural product synthesis. This review focuses on intermolecular functionalization of (cross)-conjugated cyclohexanone-derived compounds using asymmetric organocatalysis.
Article
Chemistry, Multidisciplinary
Muhammad Sohail, Fujie Tanaka
Summary: The DYKAT reactions can transform dihydrobenzofuranone derivatives into spirooxindole derivatives with high enantioselectivities and yields, regardless of the stereochemistry of the starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Fangfang Guo, Jiean Chen, Yong Huang
Summary: Recently, chiral N-heterocyclic carbenes (NHCs) have been established as powerful catalysts for enantioselective bond-forming processes via noncovalent interactions. A bifunctional NHC with an embedded hydrogen-bonding motif has been reported in this study, showing remarkable tolerance of various Michael acceptors in an asymmetric aza-conjugate addition reaction, with catalytic efficiency far exceeding that of the benchmark tertiary amine-thiourea scaffold.
Article
Chemistry, Multidisciplinary
Donglei Wang, Ying-Bo Shao, Yunrong Chen, Xiao-Song Xue, Xiaoyu Yang
Summary: An efficient method for the asymmetric synthesis of planar-chiral macrocycles (paracyclophanes) has been developed using chiral phosphoric acid catalysis for enantioselective electrophilic aromatic aminations with azodicarboxylates. This method allows for the synthesis of a wide range of chiral macrocycles with varying ring sizes and functional groups, achieving high yields and enantioselectivities. The mechanism and origins of the stereoselectivities of these reactions were investigated through experimental studies and computational calculations. Preliminary utilization of the planar-chiral macrocycle as a chiral organocatalyst demonstrated the potential applications of these novel chiral skeletons.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Laura A. Bryant, Kenneth Shankland, Hannah E. Straker, Callum D. Johnston, Nicholas R. Lees, Alexander J. A. Cobb
Summary: The article describes a rare organocatalytic intramolecular cyclization of resorcinols with a high enantioselectivity using a specific organocatalyst. The obtained bicyclic resorcinols show excellent utility in the synthesis of cannabinoid-like compounds, and exhibit anticonvulsant activity.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Vasco Corti, Mathias Kirk Thaegersen, Valdemar Juel Enemaerke, Nomaan M. Rezayee, Casper L. Barlose, Karl Anker Jorgensen
Summary: The first atroposelective aminocatalytic methodology for the construction of C-N atropisomers is described. By directly coupling indole-2-carboxaldehydes to ortho-quinones, a new library of functionalized and enantioenriched C-N atropisomers was obtained using a designed and synthesized aminocatalyst. The synthetic utility of these atropisomers was demonstrated through various transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Will C. Hartley, Florian Schiel, Elena Ermini, Paolo Melchiorre
Summary: We reported a catalytic asymmetric protocol for preparing chiral pyrrolidinones via a radical pathway. This chemistry combines photoredox catalysis and Lewis base catalysis to achieve the first example of asymmetric radical conjugate addition to alpha,beta-unsaturated anhydrides and esters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Adrien Quintard
Summary: This manuscript reviews recent transformations developed through combining cheap iron or copper complexes with organo-catalysis, overcoming limitations of single catalyst activation modes and achieving considerable synthetic economies. The strategies for efficiently combining different catalysts and resulting synthetic applications are discussed.
ISRAEL JOURNAL OF CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Adrien Quintard
Summary: In the past decade, multi-catalysis has become a popular alternative to traditional methods, offering rapid, efficient, and environmentally friendly ways to synthesize complex organic molecules. The use of iron-based catalysts has emerged as a cost-effective solution, with the added benefit of diverse reactivity features that expand the chemist's toolbox. These advantages position iron-based multi-catalysis as a leading technology for the future.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Adrien Quintard
Summary: Selective copper catalysis activation of ketoacids, particularly bio-sourced 1,3-acetonedicarboxylic acid, and condensation with aldehydes under mild conditions, can lead to rapid preparation of natural product fragments and significant progress in this field through multicatalytic combination with organocatalysis. Additionally, cascade incorporation of fluorine offers new synthetic analogues with improved properties for a wide range of applications.
Article
Chemistry, Organic
Titouan Desrues, Xueyang Liu, Jean-Marc Pons, Valerie Monnier, Jean-Arthur Amalian, Laurence Charles, Adrien Quintard, Cyril Bressy
Summary: This study introduces a new method for the enantioselective synthesis of tertiary alcohols through a chiral isothiourea catalyzed selective acylation of adjacent secondary alcohols, allowing for the preparation of highly enantioenriched monoesters and starting diols. The approach enables the kinetic resolution of racemic diastereoenriched secondary/tertiary diols with s-values exceeding 200.
Article
Chemistry, Multidisciplinary
Titouan Desrues, Jeremy Merad, Daniela Andrei, Jean-Marc Pons, Jean-Luc Parrain, Maurice Medebielle, Adrien Quintard, Cyril Bressy
Summary: This study reported an enantioselective organocatalyzed acylation of alpha,alpha-difluorohydrins using a commercially available chiral isothiourea, greatly improving the enantioselectivity of the kinetic resolution process through electrostatic fluorine-cation interactions. The method allows for the synthesis of various fluorinated alcohols with exquisite enantiocontrol, such as 4,4-difluoro-1,3-diols, as well as demonstrated compatibility between aromatic and fluorinated groups in providing enantioenriched adducts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Na Shao, Xueyang Liu, Valerie Monnier, Laurence Charles, Jean Rodriguez, Cyril Bressy, Adrien Quintard
Summary: The authors developed a simple strategy to synthesize enantioenriched complex acyclic stereotriads with fluorinated tetrasubstituted stereocenters, by combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution in two unprecedented steps. The aldol-Tishchenko reaction directly generated a large panel of acyclic 1,3-diols possessing a fluorinated tetrasubstituted stereocenter with excellent diastereocontrol, while the subsequent organocatalyzed kinetic resolution produced the desired enantioenriched stereotriads with high selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Na Shao, Valerie Monnier, Laurence Charles, Jean Rodriguez, Cyril Bressy, Adrien Quintard
Summary: This study reports a multicatalytic strategy for the synthesis of a new type of scaffold containing a tetrasubstituted stereocenter embedded in fluorohydrin motifs. The method involves organocatalyzed fluorination and diastereoselective aldol reaction, resulting in the stereoselective synthesis of fluorinated 1,3-diols.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xueyang Liu, Jean-Marc Pons, Valerie Monnier, Laurence Charles, Adrien Quintard, Cyril Bressy
Summary: This paper describes an efficient enantioselective kinetic resolution method for the separation of secondary alcohols with a quaternary stereocenter. It utilizes a commercially available chiral isothiourea organocatalyst and achieves high levels of stereoselectivity in a wide range.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Nanoscience & Nanotechnology
Enzo Olivieri, Baptiste Gasch, Guilhem Quintard, Jean-Valere Naubron, Adrien Quintard
Summary: This article reports the use of trichloroacetic acid (TCA) as fuel to create time-controlled materials that can reversibly switch between gel and solution states. These materials have interesting time-dependent properties and can be used in the generation of remoldable objects, erasing ink, chiroptical switches, and new types of electrical systems.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Organic
Aleena Thomas, Baptiste Gasch, Enzo Olivieri, Adrien Quintard
Summary: This study presents a purification technique for amines by triggering their salt formation with trichloroacetic acid (TCA) and subsequently liberating pure amines through decarboxylation, reducing the number of operations and waste generation.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Enzo Olivieri, Na Shao, Roselyne Rosas, Jean-Valere Naubron, Adrien Quintard
Summary: In this study, we have developed a rotating molecular switch based on metal-catalyzed reversible (de)hydrogenation. This switch can switch between alcohol and ketone through reversible (de)hydrogenation reactions. The absence of waste accumulation in this chemical-stimuli-driven switch is of great significance and has potential applications in the design of efficient complex molecular machines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Na Shao, Jean Rodriguez, Adrien Quintard
Summary: Apratoxin A is a potent anticancer natural product. The synthesis of its key compound has always been a challenge in organic chemistry. By combining different catalytic reactions, the key polyketide fragment can be prepared rapidly. This method allows for the preparation of the apratoxin A fragment in just six steps, representing the shortest route to this polyketide.
Article
Chemistry, Multidisciplinary
Vincent Verdoot, Adrien Quintard
Summary: The implementation of new activated carboxylic acids is crucial for reversible chemical systems. Using 1,3-acetonedicarboxylic acid, the pH of aqueous solutions can be decreased and then autonomously evolve over time back to a higher value through decarboxylation. This process generates less waste and decreases toxicity, making it suitable for complex chemically fuelled systems.
Article
Chemistry, Multidisciplinary
Enzo Olivieri, Adrien Quintard
Summary: Dissipative systems are based on the supply of energy and its dissipation through fuel pulses and decomposition, allowing for repetitive physical or biological functions. Researchers have attempted to apply these principles to synthetic systems, but the accumulation of waste from fuel decomposition hampers the system's operation. To solve this issue, trichloroacetic acid has emerged as a preferred fuel choice, altering the system's acidity reversibly and liberating volatile chloroform and CO2 upon fuel decomposition. This Perspective highlights the advantages of this fuel and its successful applications.
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Multidisciplinary
Na Shao, Xueyang Liu, Valerie Monnier, Laurence Charles, Jean Rodriguez, Cyril Bressy, Adrien Quintard
Summary: This research presents a simple strategy for the elaboration of enantioenriched complex acyclic stereotriads through a sequence of two unprecedented steps. By combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution, compounds with fluorinated tetrasubstituted stereocenters can be efficiently synthesized with excellent selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
