Article
Chemistry, Applied
Bo Chen, Chang-Sheng Kuai, Jian-Xing Xu, Xiao-Feng Wu
Summary: A Mn(III)-promoted double carbonylation reaction using anilines and alkylborates or Hantzsch esters has been developed for the synthesis of alkyl alpha-ketoamides with excellent selectivity. The method provides a broad range of derivatives in moderate to good yields.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
An-Jing Wang, Chun-Yan She, Yu-Die Zhang, Li-Han Zhao, Wen-Ming Shu, Wei-Chu Yu
Summary: A copper(II)-promoted denitrogenation/oxidation reaction was developed to prepare primary alpha-ketoamides using alpha-azido ketones as substrate and TEMPO as oxidant. In this reaction, alpha-azido ketones were denitrogenated in situ to form an imino ketone intermediate, which then underwent radical addition and radical migration to yield alpha-ketoamides. The imino ketone intermediate plays a crucial role in this reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jianting Ma, Xue Cui, Junyu Xu, Yinfeng Tan, Yan Wang, Xuesong Wang, Youbin Li
Summary: A one-pot strategy using ynamides as coupling reagents has been developed for the formation of alpha-keto amide bonds under extremely mild reaction conditions. Diversely structural alpha-ketoamides were obtained in up to 98% yield for 36 examples. This reaction offers practical coupling procedure, wide functional group tolerance, and extremely mild conditions, with potential applications in synthetic and medicinal chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yonghong Liu, Shuangjie Lin, Dandan Zhang, Bingkun Song, Yunhe Jin, Erjun Hao, Lei Shi
Summary: This work presents a photochemical Nozaki-Hiyama-Kishi coupling reaction enabled by bioinspired Hantzsch ester, which serves as both an electron and a proton donor. The method offers a mild and operationally easy approach that shows broad compatibility with various alkenyl triflates and aldehydes.
Article
Chemistry, Organic
Feng Zhao, Na Meng, Ting Sun, Jiangwei Wen, Xiaohui Zhao, Wei Wei
Summary: A mild and environmentally benign electrochemical strategy has been developed to synthesize alpha-ketoamides via decarboxylative coupling reaction of alpha-keto acids with isocyanides and water. This efficient reaction can be conducted under constant current electrolysis without the need for transition metal catalysts or external oxidants. Mechanistic studies indicate that water not only serves as a starting material for constructing alpha-ketoamides but also plays a crucial role in promoting the electrochemical redox of alpha-keto acids.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Rui Shao, Haixia Zhao, Shumin Ding, Lianjie Li, Chen Chen, Jian Wang, Yongjia Shang
Summary: In this study, a silver-promoted [3+4] cycloaddition reaction between alpha-isocyanoacetates and anthranils was developed, leading to the synthesis of benzo[d][1,3]diazepinones. Mechanistic studies revealed an oxygen migration rearrangement process involved in this dearomative cycloaddition reaction. Additionally, catalytic conditions efficiently yielded benzo[d][1,3]diazepinones, while tolerating a wide range of functional groups under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Gong-Qing Liu, Wei Yi, Peng-Fei Wang, Ji Liu, Meng Ma, Da-Yun Hao, Liang Ming, Yong Ling
Summary: A novel reaction system has been developed for the oxidative coupling of diselenides with vinylarenes under visible light irradiation, providing a range of alpha-aryl and alpha-alkyl selenomethyl ketones with high yields and excellent compatibility with various functional groups. The use of a green solvent, air as an oxidant, and natural sunlight as a sustainable energy source sets this protocol apart from previous methods, making it an attractive option for the synthesis of medicinal and agrochemical compounds.
Article
Chemistry, Organic
Sajjad Ahmed, Mohammad Yaqoob Bhat, Feroze Hussain, Qazi Naveed Ahmed
Summary: In this study, the activation of diphenyl phosphite by BF3/BF4(-) resulted in the formation of thionium ions from aldehydes and thiophenols. These reactive species then reacted with in situ generated phenol, leading to the synthesis of diarylmethyl thioethers. It was found that the addition of external phenol in the reaction yielded unsymmetrical gem-diarylmethyl thioethers in good yields.
Article
Chemistry, Multidisciplinary
Matthew J. Evans, Mathew D. Anker, Claire L. McMullin, Martyn P. Coles
Summary: In this study, the reaction between potassium aluminyl and various isocyanide substrates was investigated. Different products were obtained depending on the isocyanide used. Degradation of isocyanide and formation of isomeric compounds were observed with tBu-NC. C-3-homologated product and dearomatisation of one aromatic substituent were observed with Dmp-NC. Both C-2- and C-3-homologation products were obtained with Ad-NC, showing control over the chain growth process.
Article
Chemistry, Multidisciplinary
Xin Qin, Jinhai Zhang, Zhan-Yong Wang, Yimei Song, Yixiao Yang, Wenhai Zhang, Hongxin Liu
Summary: In this study, a aldol/Michael cascade reaction on the beta,gamma-positions of alpha,beta-unsaturated ketones with ketoamides to construct bicyclic lactams via DBU catalysis has been developed. The substrates exhibited high regio- and diastereoselectivities and yielded moderate to good results (32 examples). Control experiments showed that the hydrogen of the amide played a key role.
Article
Chemistry, Organic
Bowen Li, Gregory P. Tochtrop
Summary: The article presents a method for transforming simple aryl halides into highly functionalized intermediates, which can then be converted to valuable compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jiwei Wu, Yuting Zhang, Jingyi Yang, Lingxiang Yu, Shaoqing Zhang, Jie Zhou, Zirong Li, Xiaolan Xu, Huajian Xu
Summary: A novel method for the synthesis of formamides through the decarboxylative N-formylation of amines with glyoxylic acid has been developed. This method provides an efficient protocol for the synthesis of various formamides with moderate to excellent yields, and it can accommodate a wide range of functional groups under metal free and base free conditions. Moreover, the large-scale experiments and high chemoselectivity have shown great potential application of this strategy.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Guozhe Guo, Yong Yuan, Shuocheng Wan, Xuehui Cao, Yali Sun, Congde Huo
Summary: This study demonstrated for the first time that K2S2O8 promoted dehydrative cross-coupling reaction can synthesize a wide range of allyl sulfides, with broad substrate scopes and tolerance to various substrates, possibly involving a radical addition process.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Zhi-Yuan Gao, Yu He, Lan-Yang Li, Jie-Sheng Tian, Teck-Peng Loh
Summary: An efficient BF3-promoted cyclization reaction has been developed for the synthesis of substituted pyrroles using easily accessible alpha-amino acetals as starting materials. This metal-free process can be carried out under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Zhuo Wang, Yan Zhang, Zi-Han Wu, Yu-Long Zhao
Summary: A novel DTBP-promoted Passerini-type reaction has been developed for the efficient synthesis of alpha-acyloxycarboxamides with two identical functional groups in a single step. The wide applicability of this reaction to various isocyanides and aldehydes has been demonstrated, and the role of water in the reaction mechanism has been clarified.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(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)