Article
Chemistry, Organic
Ran Song, Zhendong Lian, Wei Feng, Tianyi Guan, Wen Si, Daoshan Yang, Jian Lv
Summary: A novel palladium-catalyzed decarboxylative O-allylation of phenols was developed. A gamma-methylidene-delta-valerolactone (GMDV) was identified as an efficient and selective allylation reagent, leading to the synthesis of allyl phenyl ethers in high yields under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
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, Multidisciplinary
Kaili Zhang, Qixing Liu, Renke He, Danyi Chen, Zhangshuang Deng, Nianyu Huang, Haifeng Zhou
Summary: The asymmetric reduction of C = O bonds of 2-arylidene cycloalkanones using a chiral ruthenium complex as a catalyst and HCOOH/Et3N as a hydrogen source resulted in high yields and high enantiomeric excess. This method is not only suitable for small-scale synthesis, but also applicable for the gram-scale synthesis of pharmaceutically important compounds.
Article
Chemistry, Multidisciplinary
Christianah Aarinola Akinnawo, Ndzondelelo Bingwa, Reinout Meijboom
Summary: Mesoporous zirconia doped with Cr exhibited outstanding reactivity and 100% selectivity in the Meerwein-Ponndorf-Verley reduction, mainly due to the intrinsic properties of its surface mesostructure rather than specific surface area. The synergistic effect between Cr and Zr species in the binary oxide facilitated the Lewis acidity-induced performance of the Cr_ZrO2 catalyst, showcasing its innovative application in the green synthesis of unsaturated alcohols.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Chun-Tai Hung, Chun-Wei Lu, Shi-Han Huang, Yin-Feng Lu, Hsiang-Chi Chou, Cheng-Che Tsai
Summary: This research utilizes chiral sulfinamides as nucleophiles in intramolecular allylic substitution and sequential aerobic oxidation with aza-Michael addition reactions, achieving good yields of chiral isoindolines and high diastereoselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Jiantao Zhang, Weiming Zhu, Peng Zhou, Cui Chen, Xianwei Li, Weibing Liu
Summary: A method for constructing γ,γ-dichloroketones through CHCl3-induced radical-dichloromethylation and 1,2-aryl migration was developed. The more electron-deficient aryl group in para-substituted unsymmetrical substrates was found to migrate preferentially. Moreover, chlorocyclopropanes could be obtained from allylic alcohols through radical-addition/1,2-aryl migration/nucleophilic substitution in a one-pot manner.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
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, Organic
Hai-Xiang Zeng, Xiao-Wen Zhang, Qi-Yang Li, Wen-Bo Liu
Summary: An enantioselective Ni-catalyzed syn-hydrocyclization reaction was developed for the synthesis of α-hydroxy γ-lactams. By using Ni(OTs)(2)·6H(2)O/(S,S)-Me-Duphos as a precatalyst and (EtO)2MeSiH as a hydride source, a wide range of enantioenriched γ-lactams with fully substituted stereogenic centers were obtained in 32-84% yields with 87.5:12.5-97:3 er. This research provides a regioselective functionalization of alkynes and offers an efficient strategy for accessing functional group-enriched chiral heterocycles.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Gargi Nikhil Vaidya, Shyam Kumar Lokhande, Sangita Dattatray Shinde, Dinesh Parshuram Satpute, Garvita Narang, Dinesh Kumar
Summary: The first 'in-water' nickel-catalyzed chemoselective C-3-allylation of (NH)-indoles employing allylic alcohols under mild conditions is reported. The use of water not only provides sustainability but also activates allylic alcohols via hydrogen bonding and stabilizes the consequent hydroxide ion. This results in facile oxidative addition and the formation of electrophilic pi-allylNi complexes leading to C-3-allyl indoles.
Article
Chemistry, Multidisciplinary
Wei Liu, Le Zhang, Ye Liu, Shi-Lu Fan, Jian-Jun Dai, Wei Tao, Hui-Xia Zhu, Hua Xiao
Summary: In this study, a consecutive S(N)2'/S(N)2'' addition of phenol to gamma-vinyl MBH carbonate was performed, leading to the formation of functionalized exocyclohexenes with excellent chemoselectivity. Additionally, using o-hydroxychalcones as pronucleophiles, a series of pharmaceutically intriguing tricyclic chromane derivatives were selectively synthesized through an S(N)2'/S(N)2''/intramolecular Diels-Alder reaction sequence with good diastereoselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Ming Chen, Yang Li, Zheng-Hui Guan
Summary: In this work, a palladium-catalyzed hydroalkoxycarbonylation and hydroxycarbonylation of cyclopent-3-en-1-ols is reported, which enables the synthesis of bridged bicyclic lactones and beta,gamma-unsaturated carboxylic acid. The reactivity of cyclopent-3-en-1-ols is controlled by the palladium catalyst and ligands. The reaction is additive-free and exhibits a broad substrate scope, allowing access to valuable synthetic and medical intermediates.
Article
Chemistry, Organic
Ying Ding, Jinguo Long, Feilong Sun, Xianjie Fang
Summary: A nickel-catalyzed isomerization/allylic cyanation of alkenyl alcohols is reported, providing a new complement to allylic substitution reactions. The use of a specific diphosphite ligand and methanol as the solvent is crucial for the success of this transformation, as demonstrated by a gram-scale regioconvergent experiment and formal synthesis of quebrachamine showcasing the high potential of this methodology.
Article
Chemistry, Organic
Karla Janardhan Reddy, Tapan Kumar Kuilya, Jin Kun Cha
Summary: Stereochemical communication was achieved in homopropargylation and homoallylation of aldehydes through the Ti-O temporary linker strategy. Propargylic and allylic alcohol derivatives were used as convenient pronucleophiles, eliminating the need for pre-fabrication of propargylation/allylation reagents. Surprisingly, 1,6-diastereoselectivity was affected by both the Grignard reagent and the reaction solvent.
Article
Chemistry, Organic
Jinping Yuan, Pankaj Jain, Jon C. Antilla
Summary: The catalytic asymmetric addition of beta,gamma-substituted allylboronates to aldehydes has been described, showing highly efficient and selective reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jinming Ma, Wendian Li, Lin He, Hui Lv
Summary: A series of novel ferrocene-based multidentate phosphine ligands have been developed for iridium-catalyzed enantioselective reduction of alpha,beta-unsaturated ketones, delivering chiral allylic alcohols in high yields and enantioselectivities. The catalyst loading required for gram scale reactions was very low, indicating excellent activity of the newly developed catalytic system for asymmetric hydrogenation of conjugated enones.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Alberto F. Garrido-Castro, Noelia Salaverri, M. Carmen Maestro, Jose Aleman
Article
Chemistry, Applied
Jorge Humbrias-Martin, M. Carmen Perez-Aguilar, Ruben Mas-Balleste, Antonella Dentoni Litta, Alessandra Lattanzi, Giorgio Della Sala, Jose A. Fernandez-Salas, Jose Aleman
ADVANCED SYNTHESIS & CATALYSIS
(2019)
Review
Chemistry, Physical
Alberto F. Garrido-Castro, M. Carmen Maestro, Jose Aleman
Review
Chemistry, Multidisciplinary
Victor Laina-Martin, Jose A. Fernandez-Salas, Jose Aleman
Summary: Cycloaddition reactions, particularly Diels-Alder reactions, are regarded as powerful methodologies for building carbon-carbon bonds. The inverse-electron-demand hetero-Diels-Alder reactions have been a significant breakthrough for synthesizing heterocyclic compounds. Among them, the organocatalytic enantioselective version has been extensively studied due to its asymmetric construction of diversely functionalized scaffolds under green chemistry conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Victor Laina-Martin, Jorge Humbrias-Martin, Ruben Mas-Balleste, Jose A. Fernandez-Salas, Jose Aleman
Summary: A highly efficient enantioselective inverse-electron-demand aza-Diels-Alder reaction has been developed, allowing the synthesis of benzofuran-fused 2-piperidinol derivatives with three contiguous stereocenters in a highly selective manner. Density functional theory calculations support the reaction mechanism and reveal the mode of action of the hydrogen-bond donor.
Article
Chemistry, Multidisciplinary
Roberto del Rio-Rodriguez, Laura Blanco, Alba Collado, Jose A. Fernandez-Salas, Jose Aleman
Summary: In this study, a nickel-catalysed reductive cross-coupling reaction between benzyl sulfonium salts and benzyl bromides is reported. Simple, stable and readily available sulfonium salts have shown their ability as leaving groups in cross-electrophile coupling, allowing the formation of challenging sp(3)-sp(3) carbon-carbon bonds for the synthesis of interesting dihydrostilbene derivatives. Additionally, benzyl tosyl derivatives have been demonstrated to be suitable substrates for reductive cross-coupling by in-situ formation of the corresponding sulfonium salt.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Leonardo Mollari, Roberto del Rio-Rodriguez, Jose A. Fernandez-Salas, Jose Aleman
Summary: This work describes the electrochemical synthesis of allyl sulfones via sulfonation of allyl trifluoroborates. The process is efficient and versatile, and does not require a mediator or additional supportive electrolyte, making it a cost-effective, safe, and environmentally friendly method for synthesizing this recognizable organic motif. The high selectivity of the sulfonation reaction is attributed to the stability of the electrochemically-generated intermediate carbocation.
Article
Chemistry, Multidisciplinary
Roberto del Rio-Rodriguez, Matthew T. Westwood, Marina Sicignano, Martin Juhl, Jose A. Fernandez-Salas, Jose Aleman, Andrew D. Smith
Summary: This study combines the photocatalytic generation of alpha-amino radicals with chiral isothiourea derived alpha,beta-unsaturated acyl ammonium intermediates. The reaction proceeds via a [3+2] radical-polar crossover mechanism to generate gamma-lactams with good yields and enantioselectivities. The enantioselective radical conjugate addition was carried out under batch and flow conditions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Roberto del Rio-Rodriguez, Lorena Fragoso-Jarillo, Alberto F. Garrido-Castro, M. Carmen Maestro, Jose A. Fernandez-Salas, Jose Aleman
Summary: We report a general, facile, and environmentally friendly electrochemical method for the Minisci-type alkylation of N-heteroarenes using widely available alkyl halides as radical precursors. The method efficiently generates primary, secondary, and tertiary alkyl radicals, which can be coupled with a variety of N-heteroarenes. The method demonstrates high functional group tolerance and has been applied in the synthesis of biologically valuable building blocks.
Article
Chemistry, Multidisciplinary
Roberto del Rio-Rodriguez, Victor Laina-Martin, Jose A. Fernandez-Salas, Jose Aleman
Summary: This highly enantioselective vinylogous Mukaiyama aldol reaction to ketoesters is catalyzed by a hydrogen-bond-donor-based bifunctional organocatalyst. Addition of silyloxy dienol ether yields multifunctional chiral tertiary alcohols with a versatile α, β-unsaturated aldehyde and excellent enantiocontrol.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Kirandeep Kaur, Jorge Humbrias-Martin, Leon Hoppmann, Jose A. Fernandez-Salas, Constantin G. Daniliuc, Jose Aleman, Olga Garcia Mancheno
Summary: The study demonstrates the first enantioselective vinylogous Mukaiyama-type dearomatisation of heteroarenes under anion-binding catalysis, utilizing a recyclable tetrakistriazole catalyst for enantiocontrol of silyl dienol ethers. This approach results in chiral heterocycles with alpha,beta-unsaturated chains showing complete regioselectivity and excellent enantioselectivities (up to 97.5 : 2.5 e.r.).
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Maria Jesus Cabrera-Afonso, Sara Cembellin, Adnane Halima-Salem, Mateo Berton, Leyre Marzo, Abdellah Miloudi, M. Carmen Maestro, Jose Aleman
Article
Chemistry, Multidisciplinary
Alberto F. Garrido-Castro, Andrea Gini, M. Carmen Maestro, Jose Aleman
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Multidisciplinary
Victor Laina-Martin, Ignacio Perez, Jose A. Fernandez-Salas, Jose Aleman
CHEMICAL COMMUNICATIONS
(2019)
