Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Jia-Hong Wu, Jian-Ping Tan, Jia-Yan Zheng, Jiajia He, Zhenlei Song, Zhishan Su, Tianli Wang
Summary: In this article, a general and modular protocol for the synthesis of axially chiral arylpyrazole scaffolds containing a phosphorus unit is described. The reaction is catalyzed by a dipeptide phosphonium salt and involves an oxidative central-to-axial chirality conversion. The reaction demonstrates excellent yields and enantioselectivities, a broad substrate scope, and a low catalyst loading, leading to the formation of axially chiral phosphine compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Tao Wang, Bo Huang, You-Qing Wang
Summary: Using chiral phosphoric acids as organocatalysts, a formal asymmetric (4+2) cycloaddition of 3-methylene isoindolinone and in situ-generated ortho-quinone methide substrates is achieved. This reaction allows the construction of spiro chroman-isoindolinones containing spiro-N,O-heterocycles with high enantioselectivity, with a broad substrate scope.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Jian-Bin Lu, Shu-Yuan Liang, Wu-Tao Gui, Zhi-Chao Chen, Wei Du, Ying-Chun Chen
Summary: A relay catalytic protocol utilizing pyrrolidine and palladium catalysis has been developed for the asymmetric synthesis of 1,3-diamine derivatives from 3-substituted 1,3-dienes, sulfuric diamide, and aldehydes. This one-pot, three-component reaction offers the advantages of high atom step economy and operational simplicity, providing an efficient and straightforward access to valuable 1,3-diamines containing quaternary and tertiary stereogenic centers with moderate to good enantioselectivity.
Article
Chemistry, Multidisciplinary
Nicolaj Inunnguaq Jessen, Maksimilian Bura, Giulio Bertuzzi, Karl Anker Jorgensen
Summary: An efficient and stereoselective synthesis of chiral cycl[3.2.2]azines has been achieved through the rational design and utilization of novel (E)-3-benzylidene-3H-pyrrolizines in iminium-ion catalysis. The method allows for incorporation of diverse enals and the obtained products can undergo selective transformations while retaining stereochemical information established in the [8+2] cycloaddition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Anup Biswas, Avisek Ghosh, Rajat Shankhdhar, Indranil Chatterjee
Summary: Chiral analogues of squaramides have proved to be efficient asymmetric catalysts in the synthesis of acyclic and cyclic chiral molecules. By utilizing several bifunctional squaramides as catalysts, a wide range of cyclic molecules bearing multiple functionalities and stereocenters have been successfully synthesized.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Nikita M. Chernov, Roman Shutov, Nadezhda Yu Sipkina, Maxim N. Krivchun, Igor P. Yakovlev
Summary: A flexible approach was developed for the synthesis of phenanthrene-like heterocycles through organocatalytic ANRORC reaction. The method allows for the generation of compounds with bright fluorescence exhibiting potential applications in various solvents. The reaction conditions are mild and suitable for a wide range of reactants.
Review
Chemistry, Organic
Mohammed Sharique, Uttam K. Tambar
Summary: Aromatic compounds are commonly used in pharmaceuticals and functional materials, leading to a focus on synthetic methods for constructing highly functionalized aromatic frameworks from acyclic precursors. Transition metal catalysis and base-promoted benzannulation reactions are widely utilized for this purpose. Recently, organocatalytic approaches such as N-heterocyclic carbene catalysis have emerged as efficient tools for the formation of complexly substituted aryl rings under mild reaction conditions.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Biochemistry & Molecular Biology
Raquel G. Soengas, Humberto Rodriguez-Solla
Summary: This review provides an overview of various methodologies for the synthesis of dienes that have emerged in the last decade, focusing on synthetic processes that meet the efficiency and sustainability requirements of modern organic chemistry.
Article
Chemistry, Organic
Tibor Penaska, Vitalii Palchykov, Erik Rakovsky, Gabriela Addova, Radovan Sebesta
Summary: The stereoselective formation of spiro oxindole pyrrolidines via formal [3+2] cycloaddition of oxindole imines with ketoesters and ketoamides was investigated, with bifunctional squaramide organocatalyst inducing enantioselectivity of up to 72% ee. Ketoamides provided alternative products, and the reaction pathway was elucidated with the help of DFT calculation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Satoru Arimitsu
Summary: This account discusses the synthesis and application of propargylic and allylic fluorides with hydroxy or carbonyl functional groups. The versatile propargylic fluorides are obtained through the Barbier-type reaction of difluoropropargyl bromides with aldehydes or chloroformates, while allylic fluorides are stereoselectively prepared using organocatalytic fluorination of dienamine intermediates. The report also explores the mechanism behind these reactions using density functional theory calculations and highlights the utility of fluorinated derivatives in the synthesis of heterocyclic compounds.
Article
Chemistry, Organic
Bubul Das, Nikita Chakraborty, Kamal Krishna Rajbongshi, Bhisma K. Patel
Summary: This article reviews different methods and approaches for the synthesis of N/O/S-heterocycles using styrene as an annulating partner in the past five years. These heterocycles are widely present in the core structure of various natural products, pharmaceuticals, and agrochemicals.
Review
Chemistry, Applied
Ahmad Saifuddin Mohamad Arshad, Mohd Nizam Mordi
Summary: Carbolines are a prominent class of tricyclic alkaloids found in natural products, and there are four different regioisomers known. Synthetic methods have been established for the construction of carboline frameworks, both requiring customized approaches for each regioisomer and unified approaches capable of generating multiple regioisomers. This review summarizes the construction of isomeric carbolines based on unified synthetic approaches.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Qi-Wen Shen, Wei Wen, Qi-Xiang Guo
Summary: The first catalytic asymmetric cascade Heck-alkylation reaction of NH2-unprotected amino acid esters with N-(2-iodophenyl)allenamides is reported in this work. The reaction proceeds smoothly using a combining catalytic system comprising a chiral aldehyde, a chiral palladium complex, and the Lewis acid ZnCl2, giving optically active alpha-alkyl tryptophan derivatives in moderate to good yields and excellent enantioselectivities. The target products can be converted into other structurally complex chiral indoles without the loss of enantioselectivities.
Article
Chemistry, Multidisciplinary
Yulin Han, Anni Qin, Qian Zhang, Xue Zhang, Hui Qian, Shengming Ma
Summary: The Rh-catalyzed reaction allows for the efficient synthesis of cis-fused bicyclic products with excellent selectivity and tolerance towards synthetically useful functional groups. The proposed mechanism involves the rapid racemization of the allene moiety in the starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Aurelie Claraz, Clemence Allain, Geraldine Masson
Summary: An electroreductive method for accessing gem-difluoroalkenes has been developed through decarboxylative/defluorinative coupling, using simple reaction conditions and carbon graphite electrodes. The metal-free transformation shows broad scope and high yields, with L-aspartic and L-glutamic acid-derived redox active esters being effective partners for the synthesis of potentially important gem-difluoroalkenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Jiyuan Lyu, Tuan Le, Aurelie Claraz, Clemence Allain, Pierre Audebert, Geraldine Masson
Summary: Efficient photocatalytic aerobic oxidative dehydrogenation reactions of N,N-disubstituted hydroxylamines to nitrones were developed using an in situ generated photocatalyst based on commercially available 3,6-dichlorotetrazine. Additionally, an oxidative (3+3) cycloaddition between an oxyallyl cation precursor and a hydroxylamine was also developed.
Article
Chemistry, Applied
Wei-Yang Ma, Emeric Montinho-Inacio, Bogdan I. Iorga, Pascal Retailleau, Xavier Moreau, Luc Neuville, Geraldine Masson
Summary: This study describes an enantioselective chiral phosphoric acid catalyzed formal [4 + 2] cycloaddition reaction between 2-benzothiazolimines and N-H-1,3-dienecarbamates. The reaction pathways diverge depending on the dienes employed, leading to different reaction products and enantioselectivities.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Thomas Varlet, Damien Bouchet, Elsa Van Elslande, Geraldine Masson
Summary: A convenient and scalable dearomative hydroacylation reaction of indoles is reported. Using readily available aldehydes as acyl sources and TBADT as an inexpensive direct HAT photocatalyst, various indole derivatives are converted into synthetically interesting 2-acylindolines with good yields and diastereoselectivity under mild conditions. An asymmetric version of the reaction is successfully developed, and an experimental mechanistic investigation provides further insights into the assumed reaction pathway.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Milane Saidah, Muhammad Idham Darussalam Mardjan, Geraldine Masson, Jean-Luc Parrain, Laurent Commeiras
Summary: The first intermolecular organocatalytic enantioselective addition of indoles to prochiral 5-membered cyclic N-acyliminium ions, generated from 5-hydroxy-alpha,beta-unsaturated pyrrolidin-2-ones, is reported hereinafter. The reaction proceeds smoothly with a range of 5-hydroxy-5-substituted-alpha,beta-unsaturated pyrrolidin-2-ones and indoles using BINOL-derived phosphoric acid catalyst to afford alpha,beta-unsaturated lactams embedding a tetrasubstituted stereogenic center in high yields and enantioselectivities.
Editorial Material
Chemistry, Organic
Geraldine Masson, Marisa C. Kozlowski, Scott J. Miller
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Editorial Material
Chemistry, Organic
Geraldine Masson, Marisa C. Kozlowski, Scott J. Miller
Editorial Material
Chemistry, Organic
Munetaka Akita, Paola Ceroni, Corey R. J. Stephenson, Geiraldine Masson
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Organic
Shelley Minteer, Jingguang Chen, Song Lin, Cathleen Crudden, Stefanie Dehnen, Prashant V. Kamat, Marisa Kozlowski, Geraldine Masson, Scott J. Miller
Editorial Material
Chemistry, Multidisciplinary
Shelley Minteer, Jingguang Chen, Song Lin, Cathleen Crudden, Stefanie Dehnen, Prashant V. Kamat, Marisa Kozlowski, Geraldine Masson, Scott J. Miller
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Organic
Damien Bouchet, Elsa Van Elslande, Geraldine Masson
Summary: A highly enantioselective formal (4 + 2)-cycloaddition between carboxylic acids and thiochalcones promoted by (+)-HBTM-2.1 isothiourea organocatalyst has been reported. The methodology involved the generation of C1-ammonium enolate intermediates and proceeded through a nucleophilic 1,4-addition-thiolactonization cascade. This method enables the stereocontrolled synthesis of sulfur-containing & delta;-thiolactones with good yields, moderate diastereoselectivity, and excellent enantiomeric excess (up to 99%), benefiting from the reactivity of uncommon electron-rich thiochalcones used as Michael acceptors.
Editorial Material
Chemistry, Analytical
Shelley Minteer, Stephanie L. Brock, Geraldine Masson, Raymond E. Schaak
ACS MEASUREMENT SCIENCE AU
(2023)
Article
Chemistry, Multidisciplinary
Emma Naulin, Marine Lombard, Vincent Gandon, Pascal Retailleau, Elsa Van Elslande, Luc Neuville, Geraldine Masson
Summary: This study reports a method for selectively controlling the regioselectivity of conjugated trienes and synthesizing chiral cis-3,6-dihydro-2H-1,2-oxazines. Modular access to three different regioisomers is achieved, and the utility of each regioisomeric cycloadduct is highlighted.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Jiyuan Lyu, Aurelie Claraz, Pascal Retailleau, Geraldine Masson
Summary: Dimeric cyclization reactions have great potential for the rapid formation of highly substituted complex cyclic molecules from simple starting materials. We report two divergent cyclodimerization reactions under simple and mild reaction conditions. The reactions produce highly substituted 1,5-dioxocanes or chromane derivatives featuring 3 contiguous tertiary stereocenters in good to high yields.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Aurelie Claraz, Geraldine Masson
Summary: This review provides an overview of the recent achievements in the construction of C(sp(3))-C(sp(3)) and C(sp(3))-C(sp(2)) bonds via cathodic reactions since 2017. It includes electrochemical reductions and convergent paired electrolyses. Cathodic processes, although less investigated, have the potential to enable alternative retrosynthetic disconnections and the discovery of new transformations.
ACS ORGANIC & INORGANIC AU
(2022)
