Article
Chemistry, Organic
Francesca Franco, Sara Meninno, Jacob Overgaard, Sergio Rossi, Maurizio Benaglia, Alessandra Lattanzi
Summary: An enantioselective synthesis method for functionalized triflones with a quaternary stereocenter has been developed, utilizing the Michael reaction and nucleophilic acyl substitution. The study highlights the potential of the triflinate anion as a leaving group for stereocontrolled postfunctionalizations.
Article
Chemistry, Multidisciplinary
Alessandra Lattanzi
Summary: The development of organocatalysis and the use of Michael addition reaction have greatly contributed to the synthesis of quaternary stereocenters and the preparation of functionalized building blocks. In this account, the authors highlight their achievements in accessing novel heterocycles with quaternary stereocenters, particularly focusing on the use of organocatalysis derived from Cinchona alkaloids. The enantioenriched heterocycles obtained were further manipulated to prepare useful compounds for downstream applications.
Article
Chemistry, Multidisciplinary
Cheng Sheng, Zheng Ling, Junzhe Xiao, Kai Yang, Xie Fang, Shengming Ma, Wanbin Zhang
Summary: In this study, enantio- and diastereoselective α-additions of 1-alkynyl ketimines with dual-copper-catalysis were successfully achieved under mild conditions, leading to the synthesis of chiral tetrasubstituted α-amino allenoates bearing a vicinal all-carbon quaternary stereocenter in high yields (up to 99% yield) with excellent enantioselectivities (up to 99% ee) and diastereoselectivities (up to >20:1 dr). The stereodivergent synthesis of the products was realized by the asymmetric α-addition reaction and the Grignard reagent promoted epimerization. Importantly, the reaction could be smoothly scaled up and applied to introduce chiral tetrasubstituted allenyl moieties into bioactive molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Chao-Huan Zhang, Qing Gao, Meng Li, Jian-Fei Wang, Chuan-Ming Yu, Bin Mao
Summary: A novel chiral phosphoric acid-catalyzed kinetic resolution was developed for the synthesis of enantioenriched organic compounds. High efficiency and selectivity were achieved through enantioselective intramolecular substitution. The method showed success at laboratory scale and in product transformations.
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, Multidisciplinary
Guan-Jun Wang, Shu-Yu Zhang, Zhen-Liang Sun, Peng Li, Tong-Mei Ding
Summary: Chiral phosphoric acid catalyzed regio- and enantioselective N-H functionalization of N-alkylaniline with pyrazolones derived ketimines as electrophiles, providing chiral pyrazolones containing a tetrasubstituted stereocenter bearing a new N,N'-acetal motif in excellent yields and high enantioselectivities. This strategy is characterized by low catalyst loading, mild conditions, and high efficiency and selectivity.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shanliang Dong, Kemiao Hong, Zhijing Zhang, Jingjing Huang, Xiongda Xie, Haoxuan Yuan, Wenhao Hu, Xinfang Xu
Summary: The construction of all-carbon quaternary stereocenters has attracted significant attention in catalytic asymmetric reactions. This study presents a rare and challenging asymmetric multi-component reaction that builds two C-C bonds on the same carbonic center to form quaternary stereocenters. The reaction is achieved through dirhodium/chiral phosphoric acid cooperative catalysis and provides a practical and atom-economic synthesis of poly-functionalized chiral ketones in good to high yields and excellent enantioselectivities. It offers an unprecedented gem-dialkylation process, which complements previous methods for constructing tertiary and quaternary stereocenters and utilizes readily available starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Fan-Tao Meng, Jing-Long Chen, Xiao-Yan Qin, Tian-Shu Zhang, Shu-Jiang Tu, Bo Jiang, Wen-Juan Hao
Summary: The new gold(I) self-relay catalysis reported involves a 3,3-rearrangement, Nazarov cyclization, and Michael addition cascade of 1,3-enyne acetates with aurones and their derived azadienes to produce densely functionalized cyclopentenones with a cyclic quaternary stereocenter. The tandem protocol shows high regioselectivity, broad substrate flexibility, and good functional group tolerance without the need for inert atmosphere protection, providing a catalytic and convergent approach for creating all-carbon stereoscopic centers.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Xinyi Ren, Lin Tang, Chaoren Shen, Huimin Li, Peng Wang, Kaiwu Dong
Summary: A palladium-catalyzed asymmetric hydroesterification-cyclization method was developed for efficient preparation of enantioenriched gamma-lactams, with good selectivities and a broad substrate scope. The correlation between multiple selectivities and N-substitutes of the amide linker in the substrate was demonstrated through crystallographic evidence and control experiments.
Article
Chemistry, Organic
Jun Chen, Zhan Shi, Ping Lu
Summary: A practical synthesis of enantioenriched indane derivatives with quaternary stereocenters was developed via sequential enantioselective reduction and C-H functionalization. Good to excellent enantioselectivity could be achieved by either the CuH-catalyzed asymmetric reduction or the Corey-Bakshi-Shibata (CBS) reduction of indanone derivatives. The strategy was further applied in syntheses of (nor)illudalane and botryane sesquiterpenoids.
Article
Chemistry, Organic
Ke-Xin Huang, Ming-Sheng Xie, Ji-Wei Sang, Gui-Rong Qu, Hai-Ming Guo
Summary: This study presents a novel Ni(II)/trisoxazoline-catalyzed asymmetric cascade reaction for the synthesis of chiral 3-amine-tetrahydrothiophene derivatives with a quaternary stereocenter, with high yields and excellent enantioselectivity. This strategy offers an efficient and convenient approach for constructing chiral thionucleoside analogues.
Article
Chemistry, Physical
Li-Xia Liu, Wen-Jun Huang, Qing-Xian Xie, Bo Wu, Chang-Bin Yu, Yong-Gui Zhou
Summary: The research proposed a new strategy for dynamic kinetic resolution, successfully achieving enantioselective separation of flavonoid compounds and forming two stereogenic centers, providing a new way for organic synthesis.
Article
Chemistry, Multidisciplinary
Katharina Roeser, Bettina Berger, Michael Widhalm, Mario Waser
Summary: An asymmetric protocol was developed to access a series of orthogonally functionalized acyclic chiral target molecules containing a quaternary stereogenic center through enantioselective alpha-alkylation catalyzed by chiral ammonium salts. Enantioselectivities up to e.r.=97.5 : 2.5 were achieved using just 1 mol % of Maruoka's spirocyclic ammonium salt catalysts, allowing for further functional group manipulations of the products.
Article
Chemistry, Organic
Lin-Ping Li, Jia-Qi Han, Yun-Ting Liu, Fan Yang, Xiong Wu, Jian-Hua Xie, Qi-Lin Zhou
Summary: This study reports a concise and efficient synthetic strategy for the rapid assembly of cis-fused octahydrophenanthrene scaffolds, resulting in the construction of compounds with an arylated all-carbon quaternary stereocenter.
Review
Chemistry, Multidisciplinary
Gengxin Wu, Jia-Rui Wu, Yan Huang, Ying-Wei Yang
Summary: Quaternary stereocenters play a crucial role in the three-dimensionality and enhanced properties of new molecules, but face challenges in their synthesis. The asymmetric allylic alkylation (AAA) has emerged as a powerful method for constructing tetrasubstituted stereocenters, offering advantages such as mild reaction conditions, effective rates, new functional group introduction, and carbon chain extension. This review outlines key considerations and recent progress in using AAA reactions for enantioselective synthesis, aiming to stimulate advancements in various areas like organic synthesis, asymmetric catalysis, C-H activation, and pharmaceutical chemistry.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Sara Meninno, Mario Carratu, Jacob Overgaard, Alessandra Lattanzi
Summary: A novel three-step four-transformation approach was developed for the synthesis of highly functionalized 5-amino-3,4-dihydro-2H-pyrrole-2-carboxylic acid esters, delivering amidines bearing three contiguous stereocenters. The entire sequence was carried out using benign solvents and metal-free conditions, demonstrating the synthetic utility of the products at scale-up.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Applied
Sara Meninno, Francesca Franco, Maurizio Benaglia, Alessandra Lattanzi
Summary: Pyrazoleamides have gained attention as reactive and practical surrogates in asymmetric catalysis, particularly in a variety of metal- and organocatalytic transformations. Their relevance has extended to photoredox catalysis and challenging stereoselective bond-forming reactions in recent years.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Sara Meninno, Rosaria Villano, Alessandra Lattanzi
Summary: A mild and convenient protocol using cheap and stable magnesium monoperphthalate (MMPP) as the oxidant was developed for the alpha-hydroxylation of alpha-substituted malonates, beta-ketoesters, and beta-ketoamides. The protocol allows for the synthesis of various compounds in good yields at room temperature.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Chiara Volpe, Sara Meninno, Carlo Crescenzi, Michele Mancinelli, Andrea Mazzanti, Alessandra Lattanzi
Summary: This study demonstrates an enantioselective one-pot catalytic strategy for the synthesis of dihydroquinoxalinones, using a combination of catalysts and intermediates to achieve high enantioselectivity in the formation of medicinally relevant heterocycles. The reusability of the organocatalyst and the mechanistic insights into the DROC process provide valuable information for further development of enantioselective synthesis strategies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Francesca Franco, Sara Meninno, Alessandra Lattanzi, Alessandra Puglisi, Maurizio Benaglia
Summary: A continuous flow approach was developed for the synthesis of alpha-trifluoromethylthiolated esters and amides using commercially available arylacetic acids and N-(trifluoromethylthio)phthalimide as the electrophilic reagent. The telescoped process resulted in good overall yield and short reaction times for the formation of alpha-substituted SCF3 amides and esters.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Francesca Franco, Sara Meninno, Jacob Overgaard, Sergio Rossi, Maurizio Benaglia, Alessandra Lattanzi
Summary: An enantioselective synthesis method for functionalized triflones with a quaternary stereocenter has been developed, utilizing the Michael reaction and nucleophilic acyl substitution. The study highlights the potential of the triflinate anion as a leaving group for stereocontrolled postfunctionalizations.
Article
Chemistry, Multidisciplinary
Alessandra Lattanzi
Summary: The development of organocatalysis and the use of Michael addition reaction have greatly contributed to the synthesis of quaternary stereocenters and the preparation of functionalized building blocks. In this account, the authors highlight their achievements in accessing novel heterocycles with quaternary stereocenters, particularly focusing on the use of organocatalysis derived from Cinchona alkaloids. The enantioenriched heterocycles obtained were further manipulated to prepare useful compounds for downstream applications.
Review
Chemistry, Organic
Sara Meninno
Summary: The depletion of finite primary fossil fuels necessitates a transformation in the chemical industry, particularly in the synthesis of added-value chemicals. Shifting from petro-based starting materials to renewable biomass-derived sources is crucial, as is designing greener processes to reduce environmental impact. Organocatalysis provides an opportunity to upgrade biomass-derived platform molecules in line with Green Chemistry principles, and this review highlights recent advancements in this emerging field.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sara Meninno, Alessandra Lattanzi
Summary: A one-pot multicomponent reaction, involving Knoevenagel reaction, asymmetric epoxidation, and domino ring-opening cyclization, has been developed for the synthesis of 3-aryl/alkyl piperazin-2-ones and morpholin-2-ones. The reaction proceeds in good yields (38-90%) and high enantioselectivity (up to 99% ee), with two out of three steps being catalyzed by a quinine derived urea. The method has also been applied to the enantioselective synthesis of a key intermediate for the antiemetic drug Aprepitant.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Simona De Vita, Sara Meninno, Lucia Capasso, Ester Colarusso, Maria Giovanna Chini, Gianluigi Lauro, Romolo Rinaldi, Annalisa De Cicco, Veronica Sian, Stefania Terracciano, Angela Nebbioso, Alessandra Lattanzi, Giuseppe Bifulco
Summary: In this study, a new series of histone deacetylase inhibitors (HDACi) with a 2-substituted 1,5-benzothiazepine scaffold were developed. The compounds showed potent HDAC inhibitory activity, especially those containing the sulphone moiety. In addition, they demonstrated cytotoxic effects on cancer cell lines and modulated histone acetyl markers.
BIOORGANIC & MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Vincenzo Battaglia, Sara Meninno, Alessandra Lattanzi
Summary: In this study, a novel and concise method for the synthesis of the commonly used antiplatelet drug Plavix was developed. Through careful optimization of reaction conditions, a high synthesis yield and selectivity were achieved.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Vincenzo Battaglia, Sara Meninno, Andrea Pellegrini, Andrea Mazzanti, Alessandra Lattanzi
Summary: An operationally simple method, called the Knoevenagel condensation/asymmetric epoxidation/dominoring-opening esterification (DROE) approach, has been developed to access a wide range of (R) and (S)-α-arylglycine esters using a single solvent and reaction vessel. The method involves commercially available aldehydes, phenylsulfonyl acetonitrile, cumyl hydroperoxide, anilines, and readily available Cinchona alkaloid-based catalysts. Density functional theory calculations revealed the significance of cooperative H-bonding interactions in achieving stereocontrol.
