Article
Chemistry, Multidisciplinary
Chao Shan, Liming Cao, Jiasheng Yang, Ruihua Cheng, Xiantong Yao, Chaoming Liang, Maolin Sun, Jinxing Ye
Summary: This study has established a highly diastereoselective continuous flow protocol under mild conditions to obtain various functionalized pyrrolidines with rapid, cost-efficient, and scalable access.
REACTION CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Organic
David A. Gutierrez, James Fettinger, K. N. Houk, Kaori Ando, Jared T. Shaw
Summary: This study describes the Lewis-acid-promoted addition of prochiral E- and Z-allyl nucleophiles to chiral alpha-alkoxy N-tosyl imines with stereochemical control, resulting in the synthesis of two isomers of clausenamide.
Article
Chemistry, Multidisciplinary
Mark A. Maskeri, Anthony J. Fernandes, Giovanni Di Mauro, Nuno Maulide, K. N. Houk
Summary: This study investigates the competition between Claisen-type reaction and (2+2) cyclization of Keteniminium ions through a combination of density functional theory and experimental investigations. The calculations reveal a small difference in the free energy barrier between the two reactions. Further investigations probe the electronics of the substrate and a competing side reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Sergio Cuesta-Galisteo, Johannes Schorgenhumer, Xiaofeng Wei, Estibaliz Merino, Cristina Nevado
Summary: This study presents a nickel-catalyzed asymmetric reductive hydroarylation method for synthesizing enantioenriched alpha-arylbenzamides. By using a BIm ligand, diethoxymethylsilane, and aryl halides, aryl groups can be selectively introduced to the internal position of the olefin, creating a new stereogenic center alpha to the N atom with neutral reagents and mild reaction conditions. This provides a straightforward route to pharmacologically relevant motifs found in anticancer drugs, SARS-CoV PLpro inhibitors, and KCNQ channel openers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Dong-Sheng Ji, Hui Liang, Kai-Xuan Yang, Zhi-Tao Feng, Yong-Chun Luo, Guo-Qiang Xu, Yucheng Gu, Peng-Fei Xu
Summary: A chemically divergent synthesis of beta-lactams and alpha-amino acid derivatives was achieved by using isothiourea (ITU) catalysis and switching solvents, demonstrating the versatility of this method.
Article
Chemistry, Multidisciplinary
Zugen Wu, Mingyue Wu, Kun Zhu, Jie Wu, Yixin Lu
Summary: Reductive alkene cross-coupling is a convenient method for creating C-C bonds from easily available alkene feedstocks. A one-pot protocol has been developed using oxalic acid as a traceless linchpin to achieve direct cross-coupling of electron-deficient alkenes. The reaction involves hydrocarboxylation followed by decarboxylative cross-coupling, and a dual-photocatalyst system is crucial for its success. This reaction allows for the efficient synthesis of bioactive molecules and provides a mild pathway for the generation of a CO2 radical anion.
Article
Chemistry, Organic
Patrick S. Fier, Riley A. Roberts, Reed T. Larson
Summary: We have developed a method for converting esters to ketones in a single step using simple reagents. This selective transformation is achieved by activating the adjacent carbon to deprotonation through the use of a transient sulfinate group on the nucleophile, allowing the formation of a carbanion that adds to the ester. This reaction is then followed by another deprotonation step to prevent further addition, and the resulting dianion spontaneously fragments the SO2 group upon quenching with water to produce the ketone product.
Article
Chemistry, Multidisciplinary
Ming Xiang, Ankan Ghosh, Michael J. Krische
Summary: Highly tractable 1-aryl-1-propynes prepared via Sonogashira coupling were utilized as chiral allylmetal pronucleophiles in ruthenium-JOSIPHOS-catalyzed enantioselective aldehyde allylations, leading to the construction of homoallylic sec-phenethyl alcohols with tertiary benzylic stereocenters. The efficiency of the process was influenced by both the steric and electronic features of aryl sulfonic acid additives that assist in forming a more selective and productive iodide-bound ruthenium catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Mengyuan Chen, Yuchen Liang, Taotao Dong, Weijian Liang, Yanping Liu, Yage Zhang, Xin Huang, Lichun Kong, Zhi-Xiang Wang, Bo Peng
Summary: The study merged the Morita-Baylis-Hillman (MBH) reaction and the [3,3]-sigmatropic rearrangement to achieve the [3,3]-rearrangement of aryl sulfoxides with alpha,beta-unsaturated nitriles, offering a new approach to prepare alpha-aryl alpha,beta-unsaturated nitriles with Z-selectivity. Control experiments and DFT calculations support a four-stage reaction sequence, including assembly, Lewis base addition, rearrangement, and E1cB-elimination, explaining the remarkable Z-selectivity of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xian-Liang Wang, Xing-Hao Yin, Jun-Zhao Xiao, Xue-Shun Jia, Liang Yin
Summary: A general synthesis of chiral 1,3-disubstituted allylsilanes was achieved through copper(I)-catalyzed asymmetric 1,4-conjugate silylation and subsequent Julia-Kocienski olefination. The prepared chiral compounds showed promising potential in asymmetric allylation reactions, with interesting match and mismatch phenomenon observed in the reaction of chiral aldehydes.
CHINESE JOURNAL OF CHEMISTRY
(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, Organic
Bram B. C. Peters, Norman Birke, Luca Massaro, Pher G. Andersson
Summary: The catalytic asymmetric hydrogenation of olefins is a powerful method for synthesizing chiral compounds. By using an iridium N,P-complex catalyst, various prochiral unsaturated amides can be efficiently reduced with high enantioselectivities. The attractive features of this method include its application in the synthesis of fenpropidin and the potential use of isomeric mixtures as starting materials.
Article
Chemistry, Physical
Yuanyuan Zhang, Yaoyu Liang, Xiaodan Zhao
Summary: The enantioselective electrophilic three-component thioarylation of alkenes using chiral selenide catalysis with free phenols as arylating sources has been disclosed. Various chiral phenols were obtained in high regio-, enantio-, and diastereoselectivities. Mechanistic studies showed that the transformation proceeded through carbon nucleophilic attack to give the products rather than the intramolecular rearrangement of phenolic ether intermediates.
Article
Chemistry, Organic
Qing Bao, Ting-Jia Sun, Yan-Ping Zhang, Zhen-Hua Wang, Yong You, Zhen-Zhen Ge, Ming-Qiang Zhou, Jian-Qiang Zhao, Wei-Cheng Yuan
Summary: A palladium-catalyzed enantioselective decarboxylative allylic alkylation of alpha-benzyl cyanoacetates with methylene cyclic carbamates has been developed for the construction of nitrile-containing acyclic quaternary carbon stereocenters with good results.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Sharad Kumbhar, Chinpiao Chen
Summary: Asymmetric allylation and vinylation of aldehydes using chromium(II)-oxazoline catalyst have been achieved, leading to high yields and enantioselectivity of homoallylic alcohols and allylic alcohols. The developed protocol offers a reliable and milder method for preparing chiral homoallylic and allylic alcohols.
CATALYSIS COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Che-Sheng Hsu, Carlos R. Goncalves, Veronica Tona, Amandine Pons, Marcel Kaiser, Nuno Maulide
Summary: The article presents a method of synthesizing amine compounds using highly electron-deficient iminium ions and highlights its broad applicability through a specific case study.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Miran Lemmerer, Margaux Riomet, Ricardo Meyrelles, Boris Maryasin, Leticia Gonzalez, Nuno Maulide
Summary: This study presents a novel direct C-C coupling process that combines Michael acceptors and Eschenmoser's salt without the need for Lewis acid catalyst. The underlying mechanism was revealed through a combination of kinetic, isotopic labeling experiments, and computational investigations, highlighting the significant role of HFIP as a superior mediator for proton-transfer events and the decisive role of the halide counterion.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Miryam Pastor, Marie Vayer, Harald Weinstabl, Nuno Maulide
Summary: The study introduces a general electrochemical method for accessing unsymmetrical 3,3-disubstituted oxindoles by direct C-H functionalization, with the oxindole fragment acting as an electrophile. This Umpolung approach eliminates the need for stoichiometric oxidants and operates under mild, environmentally friendly conditions. Importantly, it enables functionalization of these scaffolds via C-O bonds, and can be extended to C-C or C-N bond formation.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Marie Vayer, Miryam Pastor, Christiane Kofink, Nuno Maulide
Summary: An unexpected rearrangement of 3-hydroxyoxindoles into benzoxazinones using electrochemistry was reported in this study. The reaction proceeds under mild and environmentally friendly conditions, with the benzoxazinone products obtained in moderate to excellent yields. Mechanistic experiments suggest the involvement of a peroxide intermediate.
Article
Chemistry, Multidisciplinary
Miran Lemmerer, Haoqi Zhang, Anthony J. Fernandes, Tobias Fischer, Marianne Miesskes, Yi Xiao, Nuno Maulide
Summary: Herein, we present a method for the synthesis of alpha-aryl acrylamides through polar S-to-C aryl migrations induced by a Lewis basic organocatalyst. This polar process allows subsequent elimination reactions, leading to a formal aryl/hydrogen exchange, including SO2 extrusion. The reaction is selective for electron-deficient aromatic groups and can tolerate a variety of substituents on nitrogen and in the beta-position, providing useful building blocks for further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Nuno Maulide, Boris Maryasin, Phillip S. Grant, Jeremy Merad, Tobias Stopka, Juliette Sabbatani, Ricardo Meyrelles, Alexander Preinfalk, Leticia Gonzalez
Summary: This paper reports a novel stereodivergent carbonyl olefination method using thiouronium ylides as olefination reagents. It can selectively convert aldehydes into Z-alkenes with high stereoselectivity and broad substrate scope. Additionally, it was discovered that N-tosylimines can also efficiently produce E-alkenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Minghao Feng, Ivan Mosiagin, Daniel Kaiser, Boris Maryasin, Nuno Maulide
Summary: This study presents a novel strategy for the diastereo- and enantioselective synthesis of fi-amino amides through the direct coupling of carboxamides with ketimines. This innovative approach addresses key challenges in the Mannich reaction process, showcasing its significance in synthetic and biological chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Minghao Feng, Haoqi Zhang, Nuno Maulide
Summary: Compared to ketones and carboxylic esters, amides have traditionally been considered as less reactive members of the carbonyl family. However, recent research has shown that selective activation of amides under mild conditions is possible. This Minireview highlights the latest advances in this field, showcasing new strategies and breakthroughs in amide activation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Minghao Feng, Roberto Tinelli, Ricardo Meyrelles, Leticia Gonzalez, Boris Maryasin, Nuno Maulide
Summary: This study reports a practical method for the synthesis of alpha-amino acid derivatives via direct hydrative amination of activated alkynes using sulfinamides as the nitrogen source under mild conditions. Computational studies suggest that the reaction is enabled by a new type of sulfonium [2,3]-sigmatropic rearrangement.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Minghao Feng, Anthony J. J. Fernandes, Ana Sirvent, Eleonora Spinozzi, Saad Shaaban, Nuno Maulide
Summary: We present a simple method for the direct amination of unfunctionalized, native carbonyls (amides and ketones) by transferring a free amino group (NH2) from a commercially available nitrogen source. Mild conditions enable the production of primary a-amino carbonyls, allowing for diverse in situ functionalization reactions, such as peptide coupling and Pictet-Spengler cyclization, that take advantage of the presence of the unprotected primary amine.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Nuno Maulide, Irmgard Tiefenbrunner, Bogdan R. Brutiu, Tobias Stopka
Summary: We have developed an isothiouronium salt reagent for the straightforward synthesis of cyanomethyl thioesters with excellent functional group tolerance and without the need for thiols. Furthermore, we demonstrate that the obtained products can be used for amide synthesis in either a two-step or one-pot approach.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Phillip S. Grant, Ricardo Meyrelles, Oliver Gajsek, Gerhard Niederacher, Boris Maryasin, Nuno Maulide
Summary: Cationic cyclopropanation is a rare but important biosynthetic pathway involving the formation of a new sigma-C-C bond through the elimination of carbocations. Despite the historical influence of bioinspired synthetic chemistry, cationic cyclopropanation has not been widely used due to the preference of carbocations for competing elimination pathways. In this study, we conducted a synthetic and computational investigation of cationic cyclopropanation using 6,8-cycloeudesmanes as a platform, and successfully applied it to the synthesis of complex cyclopropanes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Minghao Feng, Anthony J. Fernandes, Ricardo Meyrelles, Nuno Maulide
Summary: We report a new method for preparing chiral α-amino amides by directly aminating amides using chiral sulfinamides. This method involves a [2,3]-sigmatropic rearrangement of a crucial sulfonium intermediate. Quantum chemical calculations provide predictive insights into the important E/Z selectivity of the amino-vinyloxy-sulfonium species.
Article
Chemistry, Multidisciplinary
Miran Lemmerer, Nuno Maulide
Summary: The combination of Lewis bases with alpha, beta-unsaturated carbonyls enables the in-situ generation of enolates, eliminating the need for strong Bronsted bases. This approach has been widely employed in arylation reactions in various contexts. This conceptual article provides an overview of the developed strategies, highlighting their features.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
David Just, Carlos R. Goncalves, Uros Vezonik, Daniel Kaiser, Nuno Maulide
Summary: A simple method for the direct formation of aminolactones from unactivated alkenes has been reported in this study, filling the gap in this field. The method utilizes cheap and readily available reactants, and exhibits excellent functional group tolerance and chemoselectivity. The synthetic versatility of the products has been demonstrated through a range of transformations.
