Article
Chemistry, Organic
Victoria Sinka, Daniel A. Cruz, Victor S. Martin, Juan I. Padron
Summary: The shortest enantioselective total syntheses of (+)-isolaurepinnacin and (+)-neoisoprelaurefucin were achieved using a common parallel synthetic strategy based on Prins-Peterson cyclization in their core construction. In only one step, a seven-membered ring oxacycle with the correct cis-stereochemistry ring closure and the Δ4 position of the endocyclic double bond in (+)-isolaurepinnacin was obtained. This unsaturation was also necessary to access the bromodioxabicycle in (+)-neoisoprelaurefucin.
Article
Chemistry, Physical
Augusto L. P. de Meireles, Kelly A. da Silva Rocha, Elena F. Kozhevnikova, Ivan V. Kozhevnikov, Elena V. Gusevskaya
Summary: The H3PW12O40 heteropoly acid supported on SiO2 as a catalyst and its bulk acidic cesium salt Cs2.5H0.5PW12O40 have been demonstrated to be highly active and recyclable for the Prins cyclization reaction, leading to the efficient synthesis of the valuable floral odorant Florol? from isoprenol and isovaleraldehyde. The use of dimethylcarbonate or diethylcarbonate as green reaction media, along with low catalyst loadings and moderate conditions, contribute to the sustainability of the method.
MOLECULAR CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Lada Dolejsova Sekerova, Zuzana Vavrikova, Thuy Trang Do, Eliska Vyskocilova, Libor Cerveny
Summary: Clarycet is an important fragrance used in various industrial applications. The optimal reaction conditions for its preparation were identified through two-step synthesis consisting of Prins cyclization and esterification. The experimental results demonstrated high yields of the desired product under specific reaction conditions.
RESEARCH ON CHEMICAL INTERMEDIATES
(2023)
Article
Chemistry, Multidisciplinary
Georgi R. Genov, Hiroki Takezawa, Harumi Hayakawa, Makoto Fujita
Summary: The TDDA reaction is a useful method to assemble complex molecular structures from simple precursors in a single step, but it requires careful design of substrates and harsh reaction conditions. In this study, we demonstrate an efficient and site-selective TDDA transformation within a self-assembled Pd6L4 cage. The encapsulation of substrates within the large cavity of the cage allows for enhanced cyclization rates and high selectivity for unsymmetrical substrates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Eva Vrbkova, Tomas Prejza, Miloslav Lhotka, Eliska Vyskocilova, Libor Cerveny
Summary: The Prins intramolecular cyclization of citronellal to produce isopulegol was studied using modified zeolites BETA with different Si/Al ratios and metal loadings of iron or zinc. It was found that impregnation with metal on Beta materials with Si/Al ratios of 38 and 75 increased catalytic activity, along with an increase in weak acid sites. In particular, Beta 38 with 1 wt.% iron loading showed high citronellal conversion and selectivity for isopulegol formation.
Article
Chemistry, Organic
Marvin Fresia, Thomas Lindel
Summary: The synthesis of ABCD tetracyclic partial structures of fungal indole diterpenes janthitrem B, JBIR-137, and shearinine G is reported, starting from 5-formylated indoline coupled to a dihydropyran moiety via Prins cyclization. The hydroxylated tetracyclic western half of janthitrem B was obtained in eight steps with a 10% overall yield. Alternative approaches using alkynylated precursors, including gold-catalyzed cycloisomerization, were also discussed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Laura F. Pena, Enol Lopez, Angel Sanchez-Gonzalez, Asuncion Barbero
Summary: A convenient method has been developed for the regioselective synthesis of allyl- and vinylsilyl alcohols from a common precursor by selecting suitable reaction conditions. These alcohols have been used in silyl-Prins cyclizations to prepare disubstituted oxygenated heterocycles in a one-pot sequential reaction. The reaction outcomes are highly dependent on the starting alkenylsilyl alcohol and reaction conditions, with various competitive pathways observed. However, the use of vinylsilyl alcohols has shown promising results in the preparation of differentially substituted cis-2,6-dihydropyrans.
Article
Chemistry, Multidisciplinary
Binjing Hu, Xinyi Cheng, Ying Hu, Xingchen Liu, Konstantin Karaghiosoff, Jie Li
Summary: The rhenium-catalyzed arylation-acyl cyclizations allow for the formation of polyfunctionalized indenones under mild reaction conditions, with good tolerance for various functional groups on both organomagnesium halides and enol lactones. The reaction provides a straightforward synthetic route to neolignan and (iso)pauciflorol F with complete control of the regioselectivity. Mechanistic studies revealed a sequence of syn-carborhenation and intramolecular nucleophilic addition in the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Physical
Emanuele Spatola, Federico Frateloreto, Daniele Del Giudice, Giorgio Olivo, Stefano Di Stefano
Summary: Cyclization is an important reaction in organic synthesis. The ease of this process is measured by Effective Molarity, and certain rings (5, 6 and 7-membered) are easier to form than others (>8-membered). Confinement of the cyclization reaction inside nanometric cavities can greatly facilitate the reaction by preorganizing the reagents and stabilizing transition states, thus altering the reaction's selectivity. Additionally, the use of chiral cavities allows for control over cyclization stereoselectivity. This review analyzes the examples of using nanoconfinement to improve cyclization reactions, control their selectivity, and close challenging rings.
CURRENT OPINION IN COLLOID & INTERFACE SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Efraim Reyes, Liher Prieto, Uxue Uria, Luisa Carrillo, Jose L. Vicario
Summary: The Prins reaction is a convenient method for synthesizing oxygen-containing heterocyclic compounds, especially tetrahydropyrans and tetrahydrofurans. Recent years have seen impressive improvements in its performance and scope, particularly in the development of new catalytic and enantioselective versions.
Article
Chemistry, Physical
Basile Lasne, Paivi Maki-Arvela, Atte Aho, Zuzana Vajglova, Kari Eranen, Narendra Kumar, Julian E. Sanchez-Velandia, Markus Peurla, Cecilia Mondelli, Javier Perez-Ramirez, Dmitry Yu Murzin
Summary: In this study, various heterogeneous micro- and mesoporous, acidic catalysts were examined for the selective synthesis of Florol (R). The results showed that a mildly acidic, microporous H-Beta-300 catalyst with a SiO2/Al2O3 ratio of 300 performed the best, achieving 72% selectivity and 99% conversion at 40 degrees C with a molar ratio of isoprenol to isovaleraldehyde of 1:5. More acidic zeolite catalysts exhibited slightly lower selectivity, while mesoporous catalysts with mild acidity and no strong Bronsted acid sites had the lowest selectivity.
JOURNAL OF CATALYSIS
(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
Chemistry, Organic
Haijian Wu, Peng Hong, Wenxue Xi, Jinshan Li
Summary: A new efficient [2 + 3] cyclization method using difluoroenoxysilanes and p-hydroxybenzyl alcohols has been developed to synthesize highly functionalized gem-difluorinated oxa-spirocyclohexadienones under mild conditions.
Review
Chemistry, Multidisciplinary
Jenna L. Miller, Jean-Marc I. A. Lawrence, Freddy O. Rodriguez del Rey, Paul E. Floreancig
Summary: This review primarily focuses on the application of carbon-hydrogen bond functionalizations in organic synthesis, with a particular emphasis on the mechanism, reaction development, natural product synthesis applications, approaches to catalysis, and use in enantioselective processes for hydride abstractions by quinone, oxoammonium ion, and carbocation oxidants. In addition to the commonly used quinone, oxoammonium ion, and carbocation hydride-abstracting agents, the potential of weaker ketone and triaryl borane oxidants has also been studied.
CHEMICAL SOCIETY REVIEWS
(2022)
Review
Chemistry, Multidisciplinary
Zhitong Zheng, Xu Ma, Xinpeng Cheng, Ke Zhao, Kaylaa Gutman, Tianyou Li, Liming Zhang
Summary: Homogeneous gold catalysis has seen significant development since the turn of the millennium, with oxidative gold catalysis being a vibrant subfield delivering valuable synthetic methods. This comprehensive review covers the mechanistic aspects, oxidants, and synthetic applications of oxidative gold catalysis.
Article
Chemistry, Organic
Alexander S. Burns, Christopher C. Ross, Scott D. Rychnovsky
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
Jacob C. DeForest, Renzo A. Samame, Gregory Suryn, Alexander Burtea, Scott D. Rychnovsky
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Biochemical Research Methods
Clinton Yu, Xiaorong Wang, Alexander Scott Huszagh, Rosa Viner, Eric Novitsky, Scott D. Rychnovsky, Lan Huang
MOLECULAR & CELLULAR PROTEOMICS
(2019)
Article
Chemistry, Multidisciplinary
Alexander S. Burns, Scott D. Rychnovsky
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Alexander Burtea, Jacob DeForest, Xinting Li, Scott D. Rychnovsky
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Organic
Alexander S. Burns, Charles Dooley, Paul R. Carlson, Joseph W. Ziller, Scott D. Rychnovsky
Article
Multidisciplinary Sciences
Craig Gutierrez, Ilan E. Chemmama, Haibin Mao, Clinton Yu, Ignacia Echeverria, Sarah A. Block, Scott D. Rychnovsky, Ning Zheng, Andrej Sali, Lan Huang
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2020)
Article
Chemistry, Analytical
Clinton Yu, Eric J. Novitsky, Nicholas W. Cheng, Scott D. Rychnovsky, Lan Huang
ANALYTICAL CHEMISTRY
(2020)
Article
Chemistry, Organic
Charles J. Dooley, Alexander Burtea, Christina Mitilian, Wendy T. Dao, Bo Qu, Nicholas T. Salzameda, Scott D. Rychnovsky
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Paul R. Carlson, Alexander S. Burns, Emily A. Shimizu, Shilin Wang, Scott D. Rychnovsky
Summary: The utility of the dioxasiline ring as a pi-facial directing group in the intramolecular Diels-Alder cyclization has been explored, showing robust stereocontrol across various substrates. Mechanistic investigation reveals the formation of the reactive diene through gamma deprotonation followed by [1,5] hydride shifts.
Article
Multidisciplinary Sciences
Andrew Wheat, Clinton Yu, Xiaorong Wang, Anthony M. Burke, Ilan E. Chemmama, Robyn M. Kaake, Peter Baker, Scott D. Rychnovsky, Jing Yang, Lan Huang
Summary: A robust in vivo XL-MS platform has been developed to map protein-protein interactions at a systems level, enabling the construction of the largest in vivo PPI network to date from HEK 293 cells. This advanced strategy provides a highly detailed panoramic portrait of human interactomes associated with diverse cellular pathways and can be generalized for charting protein interaction landscapes in any organisms.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Article
Chemistry, Organic
Leah J. Salituro, Jessica E. Pazienza, Scott D. Rychnovsky
Summary: This study reports the first total syntheses of strasseriolide A and B. Strasseriolide B exhibits potent activity against the wild-type malaria parasite Plasmodium falciparum and good activity against a chloroquine-resistant strain. A convergent strategy was employed, utilizing an aldehyde-acid fragment and a vinyl iodide-alcohol fragment, both prepared from chiral pool starting materials. The fragments were combined through a Yamaguchi esterification and cyclized with a Nozaki-Hiyama-Kishi reaction, resulting in the assembly of strasseriolide B in a 16-step LLS.
Article
Chemistry, Analytical
Fenglong Jiao, Clinton Yu, Andrew Wheat, Xiaorong Wang, Scott D. Rychnovsky, Lan Huang
Summary: Cross-linking mass spectrometry (XL-MS) is an emerging technology for studying protein-protein interactions and protein complex architectures. However, the current XL-MS technologies have limitations in revealing the scope and depth of cellular networks. Peptide enrichment prior to MS analysis is necessary to enhance cross-link identification for proteome-wide studies.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Organic
Charles J. Dooley, Scott D. Rychnovsky
Summary: The first total synthesis of a norsesquiterpene derived from the Illicium genus is reported. This natural product displays neurotrophic properties and has potential as a therapeutic for neurodegenerative diseases.
Article
Chemistry, Analytical
Fenglong Jiao, Leah J. Salituro, Clinton Yu, Craig B. Gutierrez, Scott D. Rychnovsky, Lan Huang
Summary: The development of MS-cleavable cross-linking mass spectrometry (XL-MS) allows for the efficient capture and identification of endogenous protein-protein interactions (PPIs) without the need for cell engineering. However, existing lysine-reactive cross-linkers have limitations in uncovering the complete PPI map. In this study, a sulfoxide-containing MS-cleavable haloacetamide-based cross-linker, DBrASO, was designed and synthesized to complement lysine-reactive reagents and expand PPI coverage at a systems-level.
ANALYTICAL CHEMISTRY
(2023)
