Review
Chemistry, Multidisciplinary
Xi Wang, Youbin Peng, Ling Zhao, Xiaohong Huo, Wanbin Zhang
Summary: Compared to the stereocontrol of the stereocenter at the allyl unit, asymmetric induction of prochiral nucleophiles is a challenging task in Pd-catalyzed asymmetric allylic substitutions due to the remote distance between the chiral catalyst and the prochiral nucleophile. Extensive efforts have been made to address this challenge through the design of chiral ligands. Recently, synergistic catalysis, including bimetallic catalysis and Pd/organocatalysis, has gained attention for its potential advantages in improving reactivity and selectivity, and providing a simple and unified method for the stereocontrol of prochiral nucleophiles. This review summarizes the history and advances in this field.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Applied
Hua Wang, He Wang, Lei Li, Xin Wang, Ran Sun, Ming-Dong Zhou
Summary: A ruthenium(II)-catalyzed hydroamination reaction of allenoates with arylamines has been developed, providing a straightforward and efficient approach to synthesize E-allylic amines with high selectivity and atom economy.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Devin P. Wood, Weiyang Guan, Song Lin
Summary: A bimetallic radical redox-relay strategy is utilized to generate alkyl radicals with titanium(III) catalysis and terminated via hydrogen atom transfer with cobalt(II) catalysis to achieve base-free isomerizations of N-Bz aziridines to N-Bz allylic amides. This reaction offers an alternative approach for the synthesis of allylic amides from alkenes through a three-step sequence, accomplishing a formal transpositional allylic amination.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Physical
Miroslav Dangalov, Adolfo Fernandez-Figueiras, Martin A. Ravutsov, Ekaterina Vakarelska, Maya K. Marinova, Nuno R. Candeias, Svilen P. Simeonov
Summary: A Ru-catalyzed isomerization reaction of Achmatowicz derivatives is reported, providing unexplored routes for diversification of the biogenic furanic platform. Mechanistic insights were studied using computational and deuterium labeling techniques. This transformation proved to be a robust tool for the synthesis of bioderived monomers and 4-keto-o-valerolactones, enabling the flexible synthesis of acetogenins. Additionally, a concise and protective group-free asymmetric total synthesis of two natural products, (S,S)-muricatacin and (S,S)-L-factor, is described.
Review
Chemistry, Multidisciplinary
Junhua Li, Yian Shi
Summary: This review provides a brief summary of the development of asymmetric hydroesterification, hydrocarboxylation, and hydroamidation with CO and its surrogates, which offer an effective and straightforward approach to optically active carboxylic acids and their derivatives.
CHEMICAL SOCIETY REVIEWS
(2022)
Review
Chemistry, Organic
Rajan Archana, Thaipparambil Aneeja, Gopinathan Anilkumar
Summary: This review provides an overview of the research progress in ruthenium-catalyzed allylic amination reactions, including a summary and analysis of the literature up to 2021.
CURRENT ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yusuke Kuroda
Summary: This study introduces a novel strategy for the [1,3]-rearrangement of imidates based on the oxidative addition of a palladium(0) catalyst, enabling the synthesis of structurally distinct allylic amides under mild and base-free conditions.
Article
Chemistry, Physical
Md Jabed Hossain, Brij Kumar Shah, Shabana Khan
Summary: In this study, a convenient method for the synthesis of amines using accessible Ce[N(SiMe3)(2)](3)(THF)(3) catalyst under mild conditions was developed. The reduction of 1 degrees and 2 degrees amides to amines was achieved with high yields. This methodology was also successfully applied for the synthesis of indole derivatives.
Article
Chemistry, Multidisciplinary
Mojtaba Hajiloo Shayegan, Zhong-Yuan Li, Xin Cui
Summary: This study achieved ligand-controlled regiodivergence for the catalytic semireduction of allenamides with excellent chemo- and stereocontrol.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jiguo Ma, Bin Gao, Guanshui Song, Ruixin Zhang, Qingfang Wang, Zi Ye, Wen-Wen Chen, Baoguo Zhao
Summary: Due to the nucleophilicity of the NH2 group, free-NH2 glycinates can react with MBH acetates to form N-allylated products. When chiral pyridoxal catalysts with an amide side chain are used, the chemoselectivity of the glycinates changes from N-allylation to alpha-C allylation. This reaction produces chiral multisubstituted glutamic acid esters with high stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Simone Scaringi, Clement Mazet
Summary: A Ru-catalyzed conjugative isomerization of remote alkenes is described, yielding branched 1,3-dienes with high yields, good regiocontrol, and high stereoselectivity. The reaction is compatible with a wide range of functional groups and heterocycles under mild conditions, and isomerization can occur over long distances. Control experiments support a metal-hydride mechanism, and two one-pot multimetallic selective catalytic sequences have been developed to showcase the synthetic potential of the process.
Article
Chemistry, Multidisciplinary
Shanxuan Wu, Zijun Huang, Xiaolin Jiang, Fachao Yan, Yuehui Li, Chen-Xia Du
Summary: An efficient method using oxofluorovanadates as catalysts has been developed for the reductive amination of CO2, resulting in the transformation of various amines into N-formylated products in moderate to excellent yields at room temperature in the presence of phenylsilane. Mechanistic studies indicate a reaction pathway initiated through F-Si interactions, with activated phenylsilane allowing for CO2 insertion and subsequent formation of the target product through amine attack.
Article
Chemistry, Multidisciplinary
Lu Xiao, Xin Chang, Hui Xu, Qi Xiong, Yanfeng Dang, Chun-Jiang Wang
Summary: Cooperative bimetallic catalysis enables regio-/stereodivergent asymmetric alpha-allylations of aldimine esters. By employing Et3B as the key activator, racemic allylic alcohols can be directly ionized to form Pd or Ir-pi-allyl species in the presence of achiral Pd or chiral Ir complexes, respectively. The reaction exhibits high regioselectivity and excellent stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ming Yu Jin, Yali Zhou, Dengmengfei Xiao, Yipeng You, Qianqian Zhen, Guanyu Tao, Peiyuan Yu, Xiangyou Xing
Summary: The mechanistic uniqueness and versatility of borrowing hydrogen catalysis provides an opportunity to investigate the controllability of a cascade reaction, and more importantly, to realize either one or both of chiral recognition and chiral induction simultaneously. In this study, using a robust Ru-catalyst, both kinetic resolution and asymmetric induction were achieved with remarkable levels of efficiency and enantioselectivity, showing the importance of catalyst-substrate pi-pi interactions in realizing stereochemical diversity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Jinguo Long, Shaomiao Xia, Ting Wang, Gui-Juan Cheng, Xianjie Fang
Summary: A regiodivergent cyanation of allylic alcohols under nickel catalysis was reported in this study, leading to the successful synthesis of challenging branched products. Dinitriles can also be obtained in good yields with high selectivity through subsequent hydrocyanation, which can be further functionalized into various compounds. Density functional theory (DFT) calculations provided insights into the role of ligands in tuning regioselectivity and reactivity.
Article
Chemistry, Multidisciplinary
Moritz E. Hansen, Samuel O. Yasmin, Susanne Wolfrum, Erick M. Carreira
Summary: The first total syntheses of tricyclic mutanobactins A and B, lipopeptides incorporating a thiazepanone, isolated from Streptococcus mutans, a member of the human oral microbiome, were reported. These natural products were rapidly delivered through a cascade of cyclization reactions using a solid-phase peptide synthesis (SPPS) based route. This versatile process was also used for a streamlined synthesis of mutanobactin D. Additionally, an independent synthesis of a truncated mutanobactin A analog, utilizing a novel thiazepanone amino acid building block, was provided.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Benedikt S. Schreib, Jacopo Margarini, Erick M. Carreira
Summary: The synthesis of picolinamides through Ritter reaction of 2-cyanopyridine with alcohols and alkenes is reported, and a range of additional heteroaryl nitriles successfully participate in the amidation reaction. The salient features of this reaction include operational simplicity and the use of inexpensive reagents. The synthetic utility of a camphene derived picolinamide is demonstrated through a palladium-catalyzed C-H arylation reaction.
Article
Chemistry, Multidisciplinary
Willi M. Amberg, Erick M. Carreira
Summary: This study presents the total synthesis of the complex molecule (+)-aberrarone using an Au-catalyzed-Sn-mediated cascade reaction, which efficiently closes four rings in the molecule. The method offers a stereoselective approach to synthesizing the natural product with a unique tetracyclic skeleton.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Viktoria C. Gerken, Erick M. Carreira
Summary: Graphitic carbon nitride (g-C3N4) is a photocatalyst used in the Giese reaction, showing excellent reusability and stability over five cycles with no changes in composition or morphology.
Article
Chemistry, Multidisciplinary
Nils Trapp, Michael Worle, Bernd Kuhn, Paul Gerber, Raffael Vorberg, Erick M. M. Carreira, Klaus Mueller
Summary: The molecular and crystal structures of 19 N-alkyl-substituted pipecolamide derivatives, including partial fluorination patterns, were presented. The different fluorination patterns in the N-alkyl group resulted in diastereomeric compounds with distinct crystal and molecular structures. The study also revealed an extraordinary conformational diversity in the various N-alkylpiperidine units, and provided insight into consistent conformational patterns and their modulation factors.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Supratim Ghosh, Avtar Changotra, David A. Petrone, Mayuko Isomura, Erick M. Carreira, Raghavan B. Sunoj
Summary: In this study, the mechanism of a chiral Ir-phosphoramidite-catalyzed asymmetric reductive deoxygenation reaction was investigated using density functional theory. It was found that Bi(OTf)3 promotes ionic and noncovalent interactions, which play a crucial role in nucleophile selectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
David M. Fischer, Henry Lindner, Willi M. Amberg, Erick M. Carreira
Summary: Intermolecular cyclopropanation of mono-, di-, and trisubstituted olefins with alpha-bromo-beta-ketoesters and alpha-bromomalonates under organophotocatalysis is reported. The transformation exhibits broad functional group tolerance, producing highly substituted cyclopropanes. Mechanistic investigations, including Stern-Volmer quenching, quantum yield determination, and deuteration experiments, provide insights into the catalytic cycle.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Marlene Fadel, Erick M. Carreira
Summary: The first total synthesis of (+)-pedrolide, a tigliane-derived diterpenoid featuring an unprecedented 5-5-6-6-3 carbon skeleton, was achieved. A key step in the synthesis involved the construction of the bicyclo[2.2.1]heptane core via an intramolecular cyclopentadiene-Diels-Alder cycloaddition. A norbornadiene was used as a surrogate for cyclopentadiene, and the unmasking of the cyclopentadiene was achieved through a complex Diels-Alder reaction cascade. This synthesis also provided a novel approach to a densely functionalized carane in an efficient and enantioselective manner.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Erick M. Carreira
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Sven M. Papidocha, Hendrik H. Bulthaupt, Erick M. Carreira
Summary: The first total synthesis of heavily oxidized cassane-type diterpenoids, neocaesalpin A, AA, and nominal neocaesalpin K, was achieved using a redox-flexible platform as a key intermediate. The synthesis involved an intermolecular Diels-Alder reaction and a novel late-stage oxidation method for furfuryl acetate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Henry Lindner, Willi M. Amberg, Erick M. Carreira
Summary: In this study, unactivated olefins are converted into alkyl azides using bench-stable NaN3 in the presence of FeCl3·6H2O under blue-light irradiation. The reaction exhibits anti-Markovnikov selectivity and can be conducted under mild ambient conditions in the presence of air and moisture.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Hendrik H. Bulthaupt, Fabian Glatz, Sven M. Papidocha, Chunyan Wu, Shawn Teh, Susanne Wolfrum, Lucia Balazova, Christian Wolfrum, Erick M. Carreira
Summary: This study reports the synthesis and enantioselectivity of a series of compounds, and reveals the stimulating effect of one of the compounds on the respiration of brown adipocytes, which has potential applications in obesity treatment.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
David M. Fischer, Manuel Freis, Willi M. Amberg, Henry Lindner, Erick M. Carreira
Summary: We have developed a method for difunctionalization of unactivated, terminal olefins using intermolecular addition of alpha-bromoketones, -esters, and -nitriles followed by formation of 4- to 6-membered heterocycles with pendant nucleophiles. The reaction can be conducted with alcohols, acids, and sulfonamides as nucleophiles, yielding products with 1,4 functional group relationships that can be further manipulated. The reaction employs a benzothiazinoquinoxaline organophotoredox catalyst at a low catalyst loading and is tolerant to air and moisture.
Article
Chemistry, Multidisciplinary
Monica Guberman, Miroslav Kosar, Anahid Omran, Erick M. Carreira, Marc Nazare, Uwe Grether
Summary: Labeled chemical probes are crucial for the development and commercialization of drugs. They play a significant role in various research phases and provide valuable tools for specific application needs. The reverse-design approach enables the generation of high-quality probes based on previously optimized small molecules, fostering collaborations between academia and industry.
Article
Chemistry, Multidisciplinary
David M. Fischer, Moritz Balkenhohl, Erick M. Carreira
Summary: The cycloisomerization of beta-, gamma-, and delta-unsaturated N-acyl sulfonamides to N-sulfonyl lactams and imidates using a CoIII(salen) catalyst with t-BuOOH or air as the oxidant is reported in this study. The method exhibits good functional group tolerance and provides a new class of cyclic building blocks. The strong solvent dependence of the transformation and the synthetic versatility of the N-sulfonyl imidate product class are highlighted.
