Article
Chemistry, Organic
Masahiro Sai
Summary: The isomerization of allylic alcohols is an important reaction, and this paper reports the development of an efficient catalytic system that allows for the isomerization of a broad range of substrates with high yields. The catalytic system was also successfully applied to a tandem reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Alessandra Casnati, Dawid Lichosyt, Bruno Lainer, Lukas Veth, Pawel Dydio
Summary: The research presents a multicatalytic method for converting alkenes, unsaturated aliphatic alcohols, and aryl boronic acids into secondary benzylic alcohols with high stereoselectivity. Prochiral allylic alcohols can also be selectively transformed into different stereoisomers of the product.
Review
Chemistry, Physical
Xue-Xin Zhang, Ying Zhang, Ling Liao, Yang Gao, Heng E. M. Su, Jin-Sheng Yu
Summary: This minireview summarizes the recent advancements in catalytic enantioselective isomerization and tandem reactions, discusses their advantages and limitations, and highlights the synthetic opportunities for further development.
Article
Chemistry, Physical
Subramanian Thiyagarajan, Raman Vijaya Sankar, Puthannur K. Anjalikrishna, Cherumuttathu H. Suresh, Chidambaram Gunanathan
Summary: This article describes a simple method for the coupling of nitriles with allylic alcohols catalyzed by a ruthenium pincer complex. Mechanistic studies were conducted to investigate the catalytic cycle. The method demonstrated tolerability towards reactive functional groups such as carbamate, sulfonate, olefin, cyano, and trifluoromethyl-substituted benzyl nitriles. Additionally, the synthesis of anipamil drug and the utility of delta-hydroxynitrile products in the synthesis and functionalization of biologically active molecules were demonstrated.
Article
Chemistry, Multidisciplinary
Kristen E. Berger, Raymond J. Martinez, Jianhan Zhou, Christopher Uyeda
Summary: Gem-dichloroalkanes can be used as precursors for asymmetric cyclopropanation reactions of alkenes. The process involves a cobalt catalyst and shows high levels of enantioselectivity for monosubstituted, 1,1-disubstituted, and internal alkenes. The reaction is compatible with alkyl-substituted carbenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Masahiro Sai
Summary: This study introduces a novel base-promoted reaction method for the diastereoselective synthesis of 1,3-diols with three contiguous stereogenic centers from allylic alcohols and aldehydes via allylic isomerization-initiated Aldol-Tishchenko reactions. Unlike traditional systems, this method utilizes readily available allylic alcohols as nucleophiles instead of enolizable aldehydes and ketones, offering a more sustainable and efficient approach to complex diol synthesis.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Organic
Shelby M. Anderson, Marcus D. Van Engen, Paul E. Floreancig
Summary: The sequential allylic alcohol transposition, carbonyl group trapping, oxocarbenium ion formation, and nucleophilic addition result in ring formation and serve as a fragment-coupling and stereocenter-generating reaction. Balancing the kinetics of productive and unproductive steps is crucial for successful applications, and solvent changes can be used to expand the scope and change the stereochemical outcomes of the processes. Mechanistic studies provide insight into the transformations and reactive species generated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Materials Science, Multidisciplinary
Xiaozhong Chen, Xingyou Han, Jing Xu, Junjie Yu, Chen Chen, Jiazhi Yang, Feng Li
Summary: A metallopolymer, Ru(p-cymene)@poly(2,2 '- BiBzlm), derived from [Ru(p- cymene)Cl]2 incorporated into poly(bibenzimidazoles), showed excellent catalytic activity for the redox isomerization of allylic alcohols to ketones. Mechanistic experiments revealed an intramolecular hydrogen shift mechanism. The catalyst was also successfully employed for the gram-scale synthesis of a biologically active molecule, and exhibited good recyclability with no significant loss in activity after five cycles.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Chemistry, Organic
Ram Singh Jat, M. Bhanuchandra
Summary: The Meyer-Schuster rearrangement and its synthetic application have been reported in this study. This reaction efficiently converts 3 degrees-propargyl alcohol to α,β-unsaturated carbonyl compounds, and can be used for the synthesis of densely arene-substituted pyrazolines bearing quaternary centers through reaction with arylhydrazine hydrochloride.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Ilya A. Bezkishko, Almaz A. Zagidullin, Mikhail N. Khrizanforov, Tatiana P. Gerasimova, Kamil A. Ivshin, Olga N. Kataeva, Yulia S. Ganushevich, Vasili A. Miluykov, Peter Loennecke, Evamarie Hey-Hawkins
Summary: A series of 3,4,5-triaryl-1,2-diphosphaferrocenes were synthesized and their structures and electrochemical properties were investigated. The results showed that these complexes exhibit good stability of the oxidized form.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Andres Alguacil, Franco Scalambra, Antonio Romerosa
Summary: In this study, a series of complexes were synthesized and characterized, and their crystal structures, including a previously published complex, were reported. The behavior of two ligands, PTA and dmoPTA, in terms of protonation and coordination, was discussed based on 15N nuclear magnetic resonance data. The construction of a library of 15N chemical shifts shed light on important features regarding the coordination of PTA and its derivatives.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yang Liu, Linghong Zhang, Yong Zhang, Shanshan Cao, Xu Ban, Yanli Yin, Xiaowei Zhao, Zhiyong Jiang
Summary: In this article, a photoredox catalytic hydrogen atom transfer (HAT) and enantioselective protonation strategy for asymmetric olefin isomerization is reported. A dual catalyst system involving a visible light photosensitizer DPZ and a chiral phosphoric acid is established, with the assistance of N-hydroxyimide to perform HAT. This strategy enables the synthesis of a wide array of allylic azaarene derivatives with high yields, ees, and E/Z ratios, highlighting its broad applicability and promising utility.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Xufang Liu, Qiang Liu
Summary: Catalytic asymmetric olefin isomerization is an important reaction for the synthesis of enantioenriched olefinic compounds with biological activity and pharmaceutical value. Highly selective catalytic methods have been developed for the synthesis of challenging chiral olefins. This perspective summarizes the major advances in this field and discusses the mechanisms, scope and limitations, and opportunities for further development.
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.
Article
Chemistry, Physical
Renat Kadyrov
Summary: An efficient and simple catalytic system has been developed for the hydrogenation of carboxylic esters using commercially available Ru-salts and imidazolium salts. This combination enables the reduction of esters to alcohols at moderate temperature and pressure, offering a practical method for alcohol synthesis.
JOURNAL OF CATALYSIS
(2023)
Review
Chemistry, Organic
Vittorio Cadierno
Summary: Recent developments in the metal-catalyzed hydrofunctionalization of alkynes with carboxylic acids are comprehensively reviewed in this study, with a focus on both inter- and intramolecular processes and their implications in the synthesis of natural products and biologically active molecules. This review also highlights the use of cascade processes for the assembly of complex heterocyclic compounds.
CURRENT ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Yersica Rios Yepes, Angela Mesias-Salazar, Alexandra Becerra, Constantin G. Daniliuc, Alberto Ramos, Rafael Fernandez-Galan, Antonio Rodriguez-Dieguez, Antonio Antinolo, Fernando Carrillo-Hermosilla, Rene S. Rojas
Summary: A series of trisubstituted guanidine ligands were used to synthesize mono- and dinuclear asymmetric methyl aluminum guanidinato compounds, which were tested as catalysts for the fixation of carbon dioxide with epoxides to give cyclic carbonates. The dinuclear complex 6 was found to be the most efficient and active catalyst for the synthesis of monosubstituted carbonates, exhibiting excellent conversions and selectivities. Additionally, the formation of some disubstituted cyclic carbonates using this dinuclear aluminum catalyst was also studied.
Article
Chemistry, Multidisciplinary
David Elorriaga, Blanca Parra-Cadenas, Antonio Antinolo, Fernando Carrillo-Hermosilla, Joaquin Garcia-Alvarez
Summary: The study demonstrated the efficient and selective fast addition of in situ generated lithium amides into carbodiimides or nitriles in ethereal green solvents, allowing for the successful synthesis of guanidines or amidines under air/moisture at room temperature without the need for isolation or purification of any halfway reaction intermediate. This environmentally-friendly protocol shows potential for applied synthesis of highly-substituted iminic-type fine chemical products.
Article
Chemistry, Physical
Victorio Cadierno
Summary: Metal-catalyzed hydrofunctionalization reactions of alkynes, especially conjugated 1,3-diynes, have been extensively studied. These reactions provide a straightforward and efficient route to functionalized olefins and various heterocyclic and carbocyclic compounds. However, the regio- and stereocontrol issues associated with conjugated 1,3-diynes make the hydrofunctionalization reactions challenging.
Article
Polymer Science
Maria Luisa Valenzuela, Desmond MacLeod-Carey, Cristian Soto Marfull, Jose Leon-Baeza, Javier Martinez, Antonio Antinolo, Fernando Carrillo
Summary: Three new guanylated cyclophosphazenes were synthesized through catalytic guanylation of different cyclophosphazenes. The resulting compounds were characterized by NMR spectroscopy and their electronic structures were investigated. These compounds exhibit a deep purple color and show charge transfer electronic transitions between aromatic rings.
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
David Elorriaga, Fernando Carrillo-Hermosilla, Blanca Parra-Cadenas, Antonio Antinolo, Joaquin Garcia-Alvarez
Summary: This study investigated the synthesis of highly selective asymmetric tertiary alcohols under the absence of external organic solvents. It was found that the reaction can be carried out at room temperature and under air/moisture, without the need for a protecting atmosphere. The results showed high chemoselectivity and the possibility of scaling up the protocol.
Article
Chemistry, Organic
Javier Francos, Victorio Cadierno
Summary: This study presents a new synthetic procedure for obtaining two previously reported donor-acceptor butadiene dyes. The reactions proceed in water under MW irradiation and the target products were characterized using various analysis methods.
Review
Biochemistry & Molecular Biology
Fernando Carrillo-Hermosilla, Rafael Fernandez-Galan, Alberto Ramos, David Elorriaga
Summary: This review focuses on the organometallic chemistry of guanidinato compounds, discussing their various coordination modes, reactivity, and applications in catalysis or materials science. It is believed that these amazing ligands offer new promises in Organometallic Chemistry.
Article
Chemistry, Inorganic & Nuclear
Alberto Ramos, Fernando Carrillo-Hermosilla, Rafael Fernandez-Galan, David Elorriaga, Jesus Naranjo, Antonio Antinolo, Daniel Garcia-Vivo
Summary: In this study, commercially available ZnEt2 was used as an efficient precatalyst for the addition of alcohols to carbodiimides, resulting in the synthesis of a wide range of isoureas under mild conditions. The bulky isourea (OMe)(NHDipp)-C(NDipp) was prepared for the first time using this catalytic method, and its structure was confirmed. The precatalyst showed high efficiency with various alcohols and diols, including those with different steric and electronic properties, and the obtained isoureas were isolated and characterized.
Review
Chemistry, Physical
Pascale Crochet, Victorio Cadierno
Summary: N-Heterocyclic carbenes (NHCs) are widely used ligands in organometallic chemistry and catalysis due to their stability and flexibility. By functionalizing NHCs with hydrophilic groups, they can be used in aqueous catalysis, which is a hot topic in Green Chemistry. This review summarizes the research on hydrophilic NHC-gold catalysts and the catalytic applications of water-soluble gold nanoparticles stabilized by hydrophilic NHCs.
