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
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, Organic
Ane Garcia-Urricelqui, Abel de Cozar, Teresa E. Campano, Antonia Mielgo, Claudio Palomo
Summary: In this study, a direct synthesis of 2,2,3-trisubstituted syn gamma-nitroaldehydes was achieved by using a cinchona-based squaric acid-derived amino acid peptide as a catalyst, providing high enantioselectivity and syn-selectivity. NMR experiments and DFT calculations were used to predict the reaction mechanism, revealing key intermolecular interactions that play a crucial role in the reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ophelie Quinonero, Clement Lemaitre, Marion Jean, Nicolas Vanthuyne, Christian Roussel, Damien Bonne, Thierry Constantieux, Cyril Bressy, Xavier Bugaut, Jean Rodriguez
Summary: This reinvestigation focused on a chiral phosphoric acid-catalyzed synthesis of polyhydroquinolines reported in 2009, revealing a lack of enantioselectivity with the use of chiral enantiopure phosphoric acid catalyst as opposed to the original report. The new Enantioselectivity results were confirmed through baseline separation of enantiomers using HPLC analyses on chiral stationary phase with UV and chiroptical detection.
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
Jia-Bin Pan, Zhi-Chun Yang, Xuan-Ge Zhang, Mao-Lin Li, Qi-Lin Zhou
Summary: Here, we present a method for enantioselective phosphoric acid catalyzed amination of ketenes generated from α-aryl-α-diazoketones. Mechanistic studies elucidated the reaction pathway and explained how the catalyst expedited the transformation and controlled the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiu-Ning Hu, Dong-Ping Wu, Ye-Peng Xu, Pei-Qiang Huang
Summary: The first organocatalytic asymmetric synthesis of an advanced intermediate of (+)-sarain A was achieved by combining organocatalytic asymmetric Michael addition reaction and a nitrogen-to-carbon chirality transfer. This method allows for the construction of three chiral centers and chemoselective reduction of a key lactam intermediate, providing a tricyclic intermediate with all necessary functionalities for further elaboration into (+)-sarain A.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Dan Hu, Si Bei Poh, Feipeng Liu, Zhifeng Tu, Xia Wang, Shenci Lu, Yu Zhao
Summary: The effect of counter-anions on enantio-control in oxidative NHC catalysis is systematically investigated in this study. The results demonstrate that the identity of counter-anions has a significant impact on the enantioselectivity of the catalytic system, and highly efficient kinetic resolution can be achieved by selecting appropriate counter-anions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Sukhmeet Kaur, Jasneet Kaur, Nasarul Islam, Amit Anand
Summary: DBU effectively catalyze the Michael addition reaction between pyridine derivatives and isatylidene malononitrile derivatives, providing adducts in 88% yield. The electronic and structural properties of the derivatives were estimated using DFT calculations.
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
En Li, Jiean Chen, Yong Huang
Summary: The Michael reaction is an important method for preparing functional molecules with a β-stereogenic center. However, the enantioselective seleno-Michael addition is still poorly explored. In this study, a highly enantioselective Michael addition reaction of alkyl selenols to enones was reported, introducing a Se atom asymmetrically to an electron-deficient double bond. A chiral bifunctional N-heterocyclic carbene (NHC)/thiourea catalyst was developed and showed remarkable selectivity in delivering chiral β-seleno ketones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Cheng Niu, Da-Ming Du
Summary: This review highlights the recent advancements in sulfa-Michael addition-triggered cascade reactions for the stereoselective synthesis of sulfur-containing compounds. It discusses various types of reactions, including sulfa-Michael/aldol, sulfa-Michael/Henry, sulfa-Michael/Michael, sulfa-Michael/Mannich and some sulfa-Michael triggered multi-step processes. The review also introduces reaction mechanisms and derivatization experiments.
Article
Chemistry, Multidisciplinary
V. Pratap Reddy Gajulapalli, Nandarapu Kumarswamyreddy, Kanduru Lokesh, Venkitasamy Kesavan
Summary: Utilizing a L-proline derived bifunctional thiourea organocatalyst, a highly functionalized 3,3'-disubstituted oxindole derivatives containing 3-acetyl coumarins and pyranocoumarin fused spirooxindoles can be synthesized with excellent yields (up to 95%) and enantioselectivities (up to 99% ee) in a broad substrate scope.
Review
Biochemistry & Molecular Biology
Jianlin Han, Jorge Escorihuela, Santos Fustero, Aitor Landa, Vadim A. Soloshonok, Alexander Sorochinsky
Summary: This review critically discusses the literature data on the preparation of substituted GABA derivatives using the Michael addition reaction. Special attention is paid to asymmetric methods featuring synthetically useful stereochemical outcomes and operational simplicity.
Article
Chemistry, Physical
Viktoria Kozma, Zsolt Szakonyi, Gyorgy Szollosi
Summary: This study reveals the structural effects of beta-amino acids on the asymmetric Michael additions, including the impact of substituent bulkiness on selectivity, the beneficial arrangement of functional groups in cis isomers, and the influence of nitrogen substituents on reaction rate and enantioselectivity.
Article
Chemistry, Organic
Xiantang Li, Yujia Mao, Pei Fan, Chuan Wang
Summary: We have developed a nickel/TBADT cocatalyzed acyl C-H benzylation method, which allows for the synthesis of various ketones under mild reaction conditions. This protocol provides a convenient and efficient approach in synthetic chemistry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Chang Zhang, Lin Wang, Hongzhang Shi, Zhiyang Lin, Chuan Wang
Summary: Iron is shown to efficiently catalyze a reaction between alpha-trifluoromethyl alkenes and unactivated ketones, resulting in the synthesis of diverse functional-group-rich compounds. This operation is simple and does not require pre-generated organometallics.
Article
Chemistry, Physical
Bing Yuan, Decai Ding, Chuan Wang
Summary: In this study, we have successfully implemented a reductive strategy for the ring opening reaction of aryl cyclopropylketones with unactivated alkyl bromides. The nickel-catalyzed reductive Csp3-Csp3cross-coupling reaction proceeds with complete regioselectivity, bypassing the need for pregenerated organometallics and allowing for efficient synthesis of alkylated ketones with high step economy and functionality tolerance.
Article
Chemistry, Organic
Weitao Hu, Zhiyang Lin, Chuan Wang
Summary: Here, we describe a nickel-catalyzed cross-electrophile ring-opening reaction of vinyl epoxides, where aryl iodides, alkyl iodides, and benzyl chlorides can all be used as electrophilic coupling partners, providing a new approach to preparing multisubstituted allylic alcohols. This method exhibits broad substrate scope, good step-economy, high selectivity, and mild reaction conditions.
Article
Chemistry, Physical
Chuan Wang, Rui Wang, Pei Fan
Summary: We developed a highly enantioselective acyl C-H allylation reaction, which can synthesize highly enantioselective α-stereogenic β,γ-unsaturated 1,4-dicarbonyl compounds.
Article
Chemistry, Physical
Decai Ding, Linchuan Zhang, Hao Wen, Chuan Wang
Summary: Here, a cobalt-catalyzed asymmetric reductive 1,2-dicarbofunctionalization of 1,3-dienes using obromoaryl imines as a bis-electrophilic coupling partner is reported. This method provides a pathway to prepare disubstituted cis-indanes in high diastereo- and enantioselectivities under mild reaction conditions. The proposed reaction mechanism includes enantioselective intermolecular migratory insertion and diastereoselective intramolecular allylation as the key elementary steps.
Article
Chemistry, Multidisciplinary
Decai Ding, Bing Yuan, Hao Wen, Chuan Wang
Summary: Asymmetric ring opening (ARO) is a powerful tool for constructing chiral cyclic molecules with multiple stereocenters. In this article, the strategy of cross-electrophile coupling is successfully applied to the ARO reaction of oxa- and azabicyclic alkenes. By using functionalized alkyl bromides as coupling partners, highly enantioenriched 1,2-dihydronaphthalenes with full cis-selectivity can be efficiently synthesized under the catalysis of a chiral nickel complex.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Jiawei Liu, Wei Tang, Chuan Wang
Summary: Here, we report a nickel-catalyzed regio- and enantioselective ring opening reaction of 3,4-epoxy amides and esters with aromatic amines as nucleophiles. This method demonstrates high regiocontrol, diastereospecific S(N)2 reaction pathway, broad substrate scope, and mild reaction conditions, enabling the synthesis of a wide range of gamma-amino acid derivatives in a highly enantioselective manner. Notably, the selective nucleophilic attack to the C-4 position of epoxides is controlled by the directing effect of the pendant carbonyl group.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Letter
Chemistry, Organic
Bing Yuan, Chang Zhang, Haiyan Dong, Chuan Wang
Summary: By merging C-C and C-F bond cleavage, a regioselective ring opening/gem-difluoroallylation of cyclopropyl ketones with a-trifluoromethylstyrenes was developed, which proceeds under the catalysis of iron with the combination of manganese and TMSCl as the reducing agents. This reaction provides a new entry to the synthesis of carbonyl-containing gem-difluoroalkenes. Remarkably, the ketyl radical-induced selective C-C bond cleavage and the following generation of more-stable carbon-centered radicals enable complete regiocontrol of this ring opening reaction for various substitution patterns of the cyclopropane ring.
Article
Chemistry, Organic
Hao Wen, Decai Ding, Chuan Wang
Summary: In this study, a nickel-catalyzed diastereoselective cross-electrophile ring opening reaction was developed using aromatic aldehydes as the electrophilic coupling partner and Zn as the stoichiometric reductant. This reaction successfully achieved the formation of two disubstituted sp3-hybridized carbon centers, resulting in a variety of 1,2-dihydronaphthalenes with full diastereocontrol of three consecutive stereogenic centers.
Article
Chemistry, Organic
Hongqing Yao, Chuan Wang
Summary: Here, the authors present a yttrium-catalyzed regioselective ring-opening reaction between 2,3-epoxy esters and amides with amines as nucleophiles. This method offers high regiocontrol, an enantiospecific S(N)2 reaction pathway, a wide substrate scope, and mild reaction conditions, resulting in the synthesis of a broad range of regioisomerically pure alpha-hydroxy beta-amino esters and amides. Importantly, the selective nucleophilic attack at the C-3 position is controlled by the directing effect of the carbonyl group of the substrates.
Article
Chemistry, Organic
Feiyan Yang, Chuan Wang
Summary: In this study, we employ polycyclic aryl-activated alkyl ammonium triflates as the electrophilic aryl-activated alkylating agent in the nickel-catalyzed hydroxyl- or sulfonamide-directed cross-electrophile coupling reaction with phenyl benzoates, resulting in the synthesis of diverse aryl ketones under mild conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Rui Wang, Chuan Wang
Summary: By combining nickel-mediated aza-Heck cyclization and radical acyl C-H activation, a highly enantioselective imino-acylation of oxime ester-tethered alkenes with aldehydes was achieved using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst. The reaction provides a convenient route to synthesize enantioenriched pyrrolines bearing an acyl-substituted stereogenic center under mild conditions. Preliminary mechanistic studies indicate a Ni(i)/Ni(ii)/Ni(iii) catalytic sequence involving intramolecular migratory insertion of a tethered olefin into the Ni(iii)-N bond as the enantiodiscriminating step.
Article
Chemistry, Organic
Hao Wen, Decai Ding, Chuan Wang
Summary: In this study, a nickel-catalyzed diastereoselective cross-electrophile ring opening reaction of 7-oxabenzonorbornadienes with aromatic aldehydes was developed, using Zn as the stoichiometric reductant. This reaction achieved stereoselective bond formation between two disubstituted sp(3)-hybridized carbon centers, providing a variety of 1,2-dihydronaphthalenes with full diastereocontrol of three consecutive stereogenic centers.
Article
Chemistry, Organic
Hongzhang Shi, Haiyan Dong, Chuan Wang
Summary: A chromium-catalyzed reductive allylic defluorinative acylation of trifluoromethyl-substituted alkenes with acyl oxime esters has been developed, allowing for efficient synthesis of various ketones bearing a gem-difluoroalkene unit.
ORGANIC CHEMISTRY FRONTIERS
(2023)
