Review
Chemistry, Multidisciplinary
Pulluparambil Xavier Thresia Rinu, Sankaran Radhika, Gopinathan Anilkumar
Summary: The Julia-Kocienski (J-K) olefination is a modified version of Julia-Lythgoe olefination, widely used in the synthesis of E-alkenes for natural product synthesis. It has shown efficient protocols and recent developments in this area, providing a key step in the synthesis of various natural products.
Article
Chemistry, Organic
Qinyu Luo, Xiu Wang, Jinbo Hu
Summary: The introduction of fluorine atoms into a carbon-carbon double bond can significantly alter the physical, chemical, and biological properties of a target molecule. Fluorinated alkenes, which are important compounds widely used in medicinal chemistry and materials science, can be synthesized through the Julia and Julia-Kocienski reactions using a-fluorinated sulfones. This review summarizes the methods for synthesizing fluorinated alkenes through Julia and Julia-Kocienski reactions, categorizing them based on target molecules and sulfone reagents, and highlights the unique effect of fluorine substituents.
Review
Chemistry, Organic
Guna Sakaine, Zigmars Leitis, Rebeka Locmele, Gints Smits
Summary: This review summarizes the scientific literature of the past decade, focusing on the key aspects for successful execution of the olefination step. The main stereoselectivity and yield-determining aspects have been outlined, providing all the necessary information for the synthesis of Julia-Kocienski reagents as well as the most commonly used reaction optimization techniques.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Konstantinos A. A. Ouzounthanasis, Stergios R. R. Rizos, Alexandros E. E. Koumbis
Summary: The Julia-Kocienski olefination, a coupling reaction between a carbonyl component and a sulfone partner, has become an important tool in the synthetic toolbox for preparing various organic compounds. Recent studies have focused on the synthesis of trisubstituted alkenes and understanding their stereoselectivity. This review provides a comprehensive overview of the progress and developments in the application of Julia-Kocienski olefination for the synthesis of trisubstituted alkenes, which are valuable precursors for natural products, analogs, and biologically important compounds. The review also discusses key methodologies, optimal conditions, stereoselectivities, and new modifications and approaches.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Vijayan Varsha, Sankaran Radhika, Gopinathan Anilkumar
Summary: Julia-Lythgoe olefination is a reaction that involves the olefination between phenyl sulfones and aldehydes (or ketones) to produce alkenes through alcohol functionalization and reductive elimination using sodium amalgam or SmI2. This reaction is mainly used for the synthesis of E-alkenes and plays a crucial role in the total synthesis of numerous natural products. This review focuses on the applications of Julia-Lythgoe olefination in natural product synthesis, including literature up to 2021.
CURRENT ORGANIC SYNTHESIS
(2023)
Article
Chemistry, Organic
Makoto Inai, Yoshinori Ueno, Hiroto Sagara, Hitoshi Ouchi, Fumihiko Yoshimura, Toshiyuki Kan
Summary: This study presents the first total synthesis of isosilybin B (4) and introduces a synthetic strategy that utilizes the modified Julia-Kocienski olefination reaction and the construction of a quinomethide intermediate.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Mintu Rehman, Sravya Surendran, Nagendra Siddavatam, Goreti Rajendar
Summary: Modified reaction conditions were shown to enhance E-selectivity of olefins in the Julia-Kocienski reaction of aldehydes with alpha-coordinating substituents. Chelating groups in aldehydes stabilize the syn-transition state with metal ions, while weakly coordinating quaternary ammonium ions lack chelating interactions, leading to improved E-selectivity. The study systematically investigated the size of neighboring protecting groups in aldehydes and their effect on E/Z-selectivity in the Julia-Kocienski reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Narasingan Aravindan, Varathan Vinayagam, Masilamani Jeganmohan
Summary: An efficient ruthenium(II)-catalyzed tandem C-C/C-N bond formation has been developed for the synthesis of cis-fused dihydrobenzo[c]phenanthridinones using aryl amides and 7-azabenzonorbomadienes. The amide group acts as a directing and leaving group, providing easy access to pharmaceutically useful alkaloids. The reaction is compatible with various functional groups and the mechanism involves directing-group-assisted C-H activation.
Article
Chemistry, Multidisciplinary
Weiyu Li, Lei Zhou
Summary: This research reports a visible-light-driven radical 1,3-selenosulfonylation of vinyldiazo compounds with selenosulfonates, yielding various gamma-seleno allylic sulfones. The reaction was carried out at room temperature in an open flask using ethyl acetate as the solvent without the need for any photocatalysts or additives. Synthetic applications of the resulting products were demonstrated through deselenization, reduction, bromination, and allylation.
Article
Chemistry, Organic
Adam Cook, Maxwell Bezaire, Stephen G. G. Newman
Summary: Herein, a protocol is disclosed that allows for the desulfonylative olefination of beta-hydroxy, beta-keto, and beta-ethereal sulfones using a Ni-NHC catalyst. This method enables the reliable synthesis of both nonconjugated and conjugated olefins with mono, di, tri, or tetrasubstitution patterns. A brief mechanistic exploration provides evidence for the presence of both radical and organonickel intermediates in the formation of the product.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Ravichandran Logeswaran, Masilamani Jeganmohan
Summary: This paper reports an oxidative cross-coupling reaction between α,β-unsaturated compounds and unactivated alkenes via cobalt-catalyzed vinylic C-H activation. The reaction was investigated with differently functionalized unsaturated compounds and unactivated olefins, leading to the preparation of valuable amide functionalized butadienes and indenones in good yields. A possible reaction mechanism involving directed olefinic C-H activation through a base-assisted deprotonation pathway is proposed.
Article
Chemistry, Organic
Wen-Bing Qin, Wei Xiong, Ya-Shi Zhao, Kai-Zhong Fu, Lei Su, Guo-Kai Liu
Summary: An elegant tandem reaction process for converting N-allyl amide into CF2H-beta-amino alcohol was described. This method proceeded smoothly under visible light irradiation in the presence of a 3 mol % Ir complex, showing broad substrate scope and functional group tolerance. Various CF2H-beta-amino alcohols were easily accessed in good to excellent yields under mild conditions. Reliable mechanistic studies revealed the involvement of sequential difluoromethyl radical addition/carbocation trap/rearrangement in the reaction.
Article
Chemistry, Organic
Dharma Theja Nannapaneni, Kiran Chinthapally, Ishita Hatial, Brandon L. Ashfeld, Brian S. J. Blagg
Summary: An efficient seven-step procedure for the synthesis of (25R)-cholesta-5,7-diene-36,26-diol from commercially available ergosterol in a yield of 25% is described. The synthesis involves Julia-Kocienski olefination of the aldehyde with benzothiazole sulfone ester in the presence of LiHMDS followed by reduction of the alkene. This research provides important insights and potential applications.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Organic
Biplab Keshari Pandia, Chidambaram Gunanathan
Summary: The unprecedented manganese-catalyzed direct alpha-alkenylation of amides using alcohols was reported, providing alpha,beta-unsaturated amides in moderate to good yields with excellent selectivity. Mechanistic studies showed that the selective olefination is facilitated by metal-ligand cooperation, resulting in water and dihydrogen as the only byproduct, making this catalytic transformation attractive, sustainable, and environmentally benign.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Boya Feng, Guodong Zhang, Xu Feng, Yu Chen
Summary: A palladium-catalyzed decarbonylative methylation of aryl carboxylic acids using trimethylboroxine as the methylating reagent is described. The Pd(OAc)(2)/XantPhos system is compatible with a wide range of carboxylic acids and derivatives, including aroyl chloride/fluoride. The successful methylation of bioactive molecules and examples of orthogonal cross-couplings demonstrate the practicality of this method.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Organic
Diego A. Alonso, Sarah-Jayne Burlingham, Rafael Chinchilla, Gabriela Guillena, Diego J. Ramon, Matteo Tiecco
Summary: This mini-review summarizes recent advances in asymmetric organocatalysis using eutectic mixtures as a reaction medium, as well as the first enantioselective transformations using chiral eutectic solvents. The review aims to delve deep into both the synthetic aspects of asymmetric organocatalysis in eutectic mixtures and the fundamental issues crucial for the successful development of this promising yet challenging methodology.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ramon E. Millan, Jaime Rodriguez, Luis A. Sarandeses, Enrique Gomez-Bengoa, Jose Perez Sestelo
Summary: The paper presents the indium(III)-catalyzed cascade cycloisomerization reaction, which efficiently synthesizes various tricyclic heterocycles such as benzo[b]chromenes, phenanthridines, xanthenes, and spiroheterocyclic compounds with high atom economy.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Leandros P. Zorba, Eunate Egana, Enrique Gomez-Bengoa, Georgios C. Vougioukalakis
Summary: A straightforward and efficient protocol for the one-pot, ZnI2-catalyzed allenylation of terminal alkynes with pyrrolidine and ketones is described in this study. Trisubstituted allenes can be obtained under conventional heating or microwave irradiation conditions, significantly reducing reaction time. The use of a sustainable, widely available, and low-cost metal salt catalyst under solvent-free conditions allows for the efficient preparation of synthetically valuable allenes bearing various functionalities. Mechanistic experiments suggest a rate-determining [1,5]hydride transfer during the transformation of the intermediate propargylamine to the final allene.
Article
Chemistry, Multidisciplinary
Jaime Martin, Enrique Gomez-Bengoa, Alexandre Genoux, Cristina Nevado
Summary: A catalytic method for synthesizing a variety of cyclometalated (C^N)gold(III) complexes is reported. The unprecedented Rh-to-Au(III) transmetalation allows for the easy transfer of (C^N) ligands between the two metals in a redox-neutral process. The reaction uses commercially available precursors and proceeds under mild and environmentally friendly conditions. Experimental and computational studies support a multi-step transmetalation mechanism from rhodium to gold as the underlying process for these transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Giovanni M. Fusi, Zelong Lim, Stephen D. Lindell, Enrique Gomez-Bengoa, Malcolm R. Gordon, Silvia Gazzola
Summary: This study demonstrates that the isomerization of purin-2- and 6-yl Grignards to 8-yl Grignards can be stopped by conducting the reaction in dichloromethane (DCM), allowing direct reactions with various aldehydes. In addition, functionalization of purine with ketones has been achieved with the presence of LaCl3·2LiCl. Density functional theory calculations provide an explanation for the role of solvent in this chemistry, indicating that the polarity of the C-Mg bond is influenced by the solvent.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Sonia Sierra, M. Victoria Gomez, Ana Jimenez, Alexandra Pop, Cristian Silvestru, Maria Luisa Marin, Francisco Bosca, German Sastre, Enrique Gomez-Bengoa, Esteban P. Urriolabeitia
Summary: The [2+2] photocycloaddition of (Z)-2-phenyl-4-aryliden-5(4H)-oxazolones using a triplet photocatalyst has been investigated. The selective formation of cyclobutane-bis(oxazolone)s has been achieved, and the reaction mechanism has been studied using laser flash photolysis and density functional theory calculations.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Marina Perez-Palau, Nil Sanosa, Pedro Romea, Felix Urpi, Rosa Lopez, Enrique Gomez-Bengoa, Merce Font-Bardia
Summary: A new stereoselective alkylation method has been developed using titanium(IV) enolates of chiral N-acyl oxazolidinones with tert-butyl peresters from Ca-branched aliphatic carboxylic acids. The reaction proceeds through the decarboxylation of peresters and formation of alkyl radicals, resulting in alkylated adducts with excellent diastereoselectivity. Theoretical calculations explain the observed reactivity and outstanding stereocontrol, with the resulting compounds easily converted into ligands for asymmetric and catalytic transformations.
Article
Chemistry, Multidisciplinary
Victor Garcia-Vazquez, Alba Carretero Cerdan, Amparo Sanz-Marco, Enrique Gomez-Bengoa, Belen Martin-Matute
Summary: This paper introduces a novel umpolung protocol for the functionalization of silyl enol ethers and 1,3-dicarbonyl compounds using a specific brominated compound as a key reagent. The mechanism of the reaction is studied experimentally and by DFT, proposing the formation of an unusual enolonium intermediate with a halogen-bonded bromide.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Dina Scarpi, Francesco Bagni, Cristina Faggi, Asier Carral-Menoyo, Enrique Gomez-Bengoa, Ernesto G. Occhiato
Summary: Six- and seven-membered ring-fused, functionalized cyclopentadienes can be obtained in moderate to excellent yields through a cascade process involving various reactions. Depending on the treatment of the crude reaction mixtures, different types of cyclopentadienes can be obtained.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Claudia Marques, Faiza Diaba, Enrique Gomez-Bengoa, Josep Bonjoch
Summary: A synthetic approach to functionalized ABC-tricyclic framework of calyciphilline A-type alkaloids is reported, which involves radical cyclization and stereocontrolled aldol cyclization. The resulting compound serves as a building block for this class of alkaloids, and the synthesis of azatricyclic compound I constitutes a formal synthesis of himalensine A.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ciro Romano, Laura Talavera, Enrique Gomez-Bengoa, Ruben Martin
Summary: This study reports a dual catalytic manifold that allows for site-selective functionalization of unactivated sp(3) C-O bonds in cyclic acetals with aryl and alkyl halides. The reaction is initiated by an appropriate sigma*-p orbital overlap prior to sp(3) C-O cleavage, highlighting the significance of conformational flexibility in both reactivity and site selectivity. The protocol demonstrates excellent chemoselectivity, opening up new possibilities for activating strong sigma sp(3) C-O linkages.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Correction
Chemistry, Multidisciplinary
Ciro Romano, Laura Talavera, Enrique Gomez-Bengoa, Ruben Martin
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Jose A. Niguez, Sarah J. Burlingham, Rafael Chinchilla, Diego A. Alonso
Summary: In this study, (S)-(1-Pyrrolidin-2-ylmethyl)quinuclidine-1-ium bromide was synthesized from l-proline in a six-step reaction process and characterized spectroscopically and thermally.
Article
Chemistry, Multidisciplinary
Kananat Naksomboon, Enrique Gomez-Bengoa, Jaya Mehara, Jana Roithova, Edwin Otten, M. Angeles Fernandez-Ibanez
Summary: Pd-catalyzed C-H functionalization reactions of non-directed substrates have emerged as a promising alternative to the use of directing groups. A new type of S,O-ligand has been found to be highly efficient in promoting Pd-catalyzed C-H olefination reactions of non-directed arenes, although its role in the process was unclear. Through various mechanistic tools, it was discovered that C-H activation is the rate-determining step and the S,O-ligand triggers the formation of more reactive Pd cationic species, explaining the observed acceleration of the reaction. These findings provide important insights into the role of the S,O-ligand in promoting Pd-catalyzed C-H functionalization reactions.
Article
Chemistry, Multidisciplinary
Alvaro Sanz-Vidal, Daniel Gavina, Lia Sotorrios, Enrique Gomez-Bengoa, Fernando Lopez Ortiz, Maria Sanchez-Rosello, Carlos del Pozo
Summary: This novel synthesis strategy for polycyclic trifluoromethyl arenes involves a DBU-promoted tandem cycloaromatization reaction, resulting in a metal-free and air-tolerant process. It enables the synthesis of these compounds from readily available starting materials under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2021)
