Article
Chemistry, Multidisciplinary
Jana Hatzfeld, Steffen Skowaisa, Elisabeth Jackel, Julia Kaufmann, Edgar Haak
Summary: Various triaminocyclopentadienyl ruthenium complexes were synthesized from Ru-3(CO)(12) and tested for their ability to catalyze cascade conversions of propargyl alcohols. The substrate scope of catalytic cycloadditions was extended to terpenoid-derived propargyl alcohols containing an internal alkyne moiety, resulting in a wide range of cyclic terpenoid and phloroglucinol adducts obtained by complementary application of both types of catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Applied
Elisa Brambilla, Silvia Meraviglia, Edoardo Moneta, Donatella Nava, Silvia Rizzato, Giorgio Abbiati, Valentina Pirovano
Summary: A photoredox-promoted approach for the synthesis of [1,4]diazepino[1,7-a]indol-6(7H)-ones starting from N-indolyl phenylacrylamides and aroyl chlorides as radical source is reported. This method involves a cascade radical addition on C-C double bond followed by intramolecular cyclization at indole C2-position, resulting in the formation of two diastereomeric indole-fused 1,4-diazepinones characterized by a N-C(aryl) axial chirality, with yields ranging from 51% to 99%.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Chengqiang Cao, Yi Yang, Xin Li, Yunxia Liu, Hui Liu, Zengdian Zhao, Lei Chen
Summary: The reaction, catalyzed by palladium, efficiently constructs two new bonds with high yields, while the alkene group is easily functionalized, leading to the formation of products with a unique structure that is difficult to synthesize.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Tianyu Zhang, Han Zhuang, Luning Tang, Zhengyu Han, Wengang Guo, Hai Huang, Jianwei Sun
Summary: A novel intramolecular C-C formation process based on catalytic asymmetric oxetane opening by carbon nucleophiles has been developed, allowing for the rapid synthesis of valuable enantioenriched 2,3-dihydrobenzo[b]oxepines under mild conditions with good chemical efficiency and enantioselectivity. The products also serve as useful precursors to other valuable structures.
Article
Chemistry, Applied
Miguel A. Munoz-Torres, Fernando Martinez-Lara, Marta Solas, Samuel Suarez-Pantiga, Roberto Sanz
Summary: The combination of organolithium chemistry with gold catalysis offers a new synthetic strategy for accessing polysubstituted indoles and carbazoles. This method utilizes ketopyrroles as starting materials and involves a series of reactions to selectively synthesize the desired products.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Fernando Martinez-Lara, Anisley Suarez, Noelia Velasco, Samuel Suarez-Pantiga, Roberto Sanz
Summary: The gold-catalyzed transformation of propargylic glycols with thiols results in the formation of alpha-indol-3-yl alpha-((Z)-2-thioalkenyl) ketones through a complex but selective reaction mechanism. This sequence involves regioselective thiolation of indolyl diols followed by the attack of sulfur on the activated alkyne, rather than the indole. The final compounds are obtained in high yields from simple starting materials such as indolyl acyloins, ethynyl magnesium bromide, and thiols.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Xuetong Li, Alba Villar-Yanez, Charlene Ngassam Tounzoua, Jordi Benet-Buchholz, Bruno Grignard, Carles Bo, Christophe Detrembleur, Arjan W. Kleij
Summary: We have developed a silver-catalyzed cascade conversion method for the selective formation of keto-functionalized cyclic carbonates using modular alkyne-1,n-diols and carbon dioxide. This method is characterized by its operational simplicity, excellent scope of carbonate-based heterocycles, and mild reaction conditions.
Review
Chemistry, Applied
Yong-Xing Song, Da-Ming Du
Summary: The aza-Michael addition cascade reaction is an important synthetic method for constructing functionalized C-N bonds, widely used in the synthesis of chiral drugs, intermediates, and natural products. This review highlights recent developments in asymmetric synthesis, including various types of aza-Michael addition triggered cascade reactions, reaction mechanisms, and derivatization experiments.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Yunxiao Zhang, Yunhong Niu, Youyuan Guo, Jiaxin Wang, Yizhi Zhang, Shanshan Liu, Xiao Shen
Summary: In this study, photocatalyzed cascade reactions between readily available cyclopropanols and alpha-trifluoromethyl-substituted olefins were reported for the synthesis of fused gem-difluorooxetanes. Two rings and three bonds were efficiently constructed in one reaction. The reaction demonstrated broad substrate scope and the downstream transformations of the products highlighted the synthetic potential. Mechanistic study supported the presence of cascade photoredox catalysis and energy transfer catalysis/direct photo-excitation processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Physical
Bartolo Gabriele, Raffaella Mancuso, Nicola Della Ca, Lucia Veltri, Ida Ziccarelli
Summary: This article provides an overview of catalytic carbonylative double cyclization reactions, where organic substrates and carbon monoxide are sequentially activated to form two new cycles with the incorporation of carbon monoxide. It highlights the power of this synthetic methodology in the one-step synthesis of complex molecular architectures using readily available CO as the building block. The review is divided into five sections: Introduction, Functionalized Olefinic Substrates, Functionalized Acetylenic Substrates, Functionalized Halides, and Conclusions and Future Perspectives.
Article
Biochemistry & Molecular Biology
Sofia Siciliano, Elena Cini, Maurizio Taddei, Giorgia Vinciarelli
Summary: The synthesis of 2-substituted indoles from unprotected 2-alkynylanilines using Pd(OAc)(2) catalyst in 3% TPGS-750-M water was found to be sensitive to the heating mode and the MW delivery mode, with convectional heating often proving more effective than microwave dielectric heating. Additionally, a tandem Sonogashira-cyclisation reaction was successfully achieved in the nanomicellar water environment with Pd(OAc)(2)/Xphos.
Article
Chemistry, Physical
Xin-Shen Liang, Rui-Dong Li, Wei Sun, Zhong Liu, Xiao-Chen Wang
Summary: Borane-mediated hydride abstraction has been shown to be a powerful tool for the C(sp(3))-H functionalization of amines, but its activity with ethers is still unknown. In this study, we discovered this activity in 2H-chromenes and established a catalytic C(sp(3))-H functionalization reaction using silyl ketene acetals as nucleophiles.
Review
Chemistry, Organic
Pascal Matton, Steve Huvelle, Mansour Haddad, Phannarath Phansavath, Virginie Ratovelomanana-Vidal
Summary: Metal-catalyzed [2+2+2] cycloaddition is a powerful method for the rapid construction of functionalized 6-membered carbo- and heterocycles with high functional group tolerance. The reaction is usually regio- and chemoselective, but challenges remain for intermolecular reactions involving multiple alkynes.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Ajmir Khan, Luiz F. Silva, Muhammad Rabnawaz
Summary: This study presents a metal-free approach for the synthesis of seven-membered heterocycles (chromane, thiochromane) or rings fused with heterocycles (furan, indole, pyrrole, and thiophene) through the ring expansion of methylenic heterocycles mediated by the iodine(III) reagent HTIB in aqueous acetonitrile.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Vibha V. Kanale, Christopher Uyeda
Summary: Cobalt catalysts facilitate highly enantioselective ring-opening reactions of 2,5-dihydrofurans using vinylidenes. The resulting products are acyclic organozinc compounds, capable of further functionalization with an electrophile. The proposed mechanism involves the formation of a cobalt vinylidene species that adds to the alkene via a [2+2]-cycloaddition pathway, followed by ring-opening through outer-sphere & beta;-O elimination assisted by a ZnX2 Lewis acid. DFT models explain the observed stereochemical outcome by suppressing competing inner-sphere syn & beta;-H and & beta;-O elimination pathways due to the geometric constraints of the metallacycle intermediate. Cobalt catalysts also promote enantioselective ring-opening reactions of unstrained heterocycles via reductive addition of 1,1-dichloroalkenes. The resulting products are acyclic homoallylic alcohols with a vinylzinc motif, which can be further modified with an electrophile. Mechanistic studies suggest that the ring-opening occurs through outer-sphere & beta;-O elimination facilitated by a Zn(II) Lewis acid.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Editorial Material
Chemistry, Multidisciplinary
Erick M. Carreira
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Nicolas Muller, Benedikt S. Schreib, Sebastian U. Leutenegger, Erick M. Carreira
Summary: In this study, the palladium-catalyzed aminoalkynylation of electronically unbiased olefins with iodoalkynes was reported. Using the picolinamide auxiliary, the syn-selective aminoalkynylation of mono-, di-, and trisubstituted alkenes was achieved, leading to the formation of corresponding pyrrolidines in high yield and single diastereomers. The picolinamide also allowed for the rapid synthesis of functionalized olefins and subsequent Pictet-Spengler reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
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.
