Article
Chemistry, Multidisciplinary
Hui Zhu, Shengxing Wu, Bingbin Zhu, Jiacheng Li, Deyou Lan, Wenhao Xu, Gongcheng Xu, Yu Zhu, Chuanming Yu, Xinpeng Jiang
Summary: In this study, gem-difluoroallylic bicyclo[1.1.1]pentanes were synthesized through a cascade multicomponent reaction using visible light-induced defluorinative gem-difluoroallylation of [1.1.1]propellane. The methodology exhibited mild reaction conditions, wide reactant scope, and suitable functional group tolerance, making it significant in modern drug design.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Jie Shi, Li-Yun Guo, Qu-Ping Hu, Yu-Tao Liu, Qing Li, Fei Pan
Summary: A photoredox-catalyzed radical cascade reaction has been developed for the synthesis of lactam-substituted gem-difluoroalkenes, providing a simple method with good functional group tolerance and high yields.
Article
Chemistry, Organic
Jibin Li, Zheng Liang, Yuzhi Ren, Jian Gao, Ding Du
Summary: A new class of functionalized gem-difluorocyclopropanes bearing acyl groups was synthesized via the N-heterocyclic carbene catalyzed difluorocyclopropanation of alkenes with aldehydes and CF2Br2. This reaction involves a cascade three-component radical relay/intramolecular cyclization process. The protocol features metal- and photocatalyst-free reaction conditions, readily accessible starting materials, good functional group tolerance, and easy scalability. Moreover, this strategy is appealing to pharmaceutical chemistry because it is potentially useful in constructing and modifying bioactive molecules via late-stage functionalization.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Yuyang Bai, Liping Cao, Siyuan Li, Guang'an Zhang, Yingguo Liu, Fengqian Zhao, Junliang Wu
Summary: A photoredox/Lewis acid cooperative catalytic system has been developed for the construction of C-vinyl-C-Rf bonds through the dehydrative difluoroalkylation of benzyl alcohols. Various allylic gem-difluorides were obtained with moderate yields and good to excellent E/Z selectivity. Control experiments were conducted and a possible mechanism for this process was proposed.
Article
Chemistry, Organic
Yanhui Wang, Gavin Chit Tsui
Summary: A highly diastereoselective Pd(0)-catalyzed Mizoroki-Heck reaction of gem-difluoroalkenes is reported. This reaction allows for cross-coupling of a C-F and C-H bond by reacting two different alkenes through a distinct pathway. Mono-fluorinated 1,3-diene products can be synthesized with control over each alkene's geometry and good functional group tolerance.
Article
Chemistry, Organic
Yue Li, Lin Shen, Mi Zhou, Baojian Xiong, Xuemei Zhang, Zhong Lian
Summary: In this study, a copper-catalyzed four-component synthesis method for sulfonylation of styrene derivatives was developed, featuring mild reaction conditions and high yields. The robustness and potential of this method were successfully demonstrated through gram-scale reactions. A radical-involved mechanism was proposed based on experimental findings.
Article
Chemistry, Multidisciplinary
Yu-Tao Zhao, Yu-Xuan Su, Xiao-Yu Li, Liang-Liang Yang, Ming-Yao Huang, Shou-Fei Zhu
Summary: A reliable method for synthesizing chiral gem-diarylmethine boron compounds with high yield, high activity, high enantioselectivity, and broad functional group tolerance has been reported. The borane compounds synthesized by this method can be efficiently transformed into various derivatives with good stereospecificity. Mechanistic studies suggest that the coordination of the borane adduct to the rhodium catalyst interferes with the decomposition of the diazomethane, and that insertion of a rhodium carbene into the B-H bond is likely the rate-determining step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Songlin Yan, Weijie Yu, Jianye Zhang, Hongmei Fan, Zhifeng Lu, Zhenming Zhang, Tao Wang
Summary: An organic photoredox-catalyzed gem-difluoroallylation of alpha-trifluoromethyl alkenes with alkyl iodides via C-F bond cleavage for the synthesis of gem-difluoroalkene derivatives is reported. The transition-metal-free transformation utilized a readily available organic dye as the sole photocatalyst and provided good to high yields with a variety of iodides, including primary, secondary, and tertiary alkyl iodides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Bin Wang, Cui-Tian Wang, Xue-Song Li, Xue-Yuan Liu, Yong-Min Liang
Summary: Here, we report a novel and efficient photoredox catalytic radical addition/defluoroalkylation coupling reaction between primary amines and trifluoromethyl-substituted alkenes. A series of gem-difluoroalkenes were synthesized through C-N bond cleavage of α-3°, α-2°, and α-1° amines under visible light irradiation. This reaction exhibits a broad substrate scope and excellent functional group tolerance.
Article
Chemistry, Multidisciplinary
Sebastian Peil, Alejandro Gutierrez Gonzalez, Markus Leutzsch, Alois Fuerstner
Summary: This study demonstrates the highly unorthodox hydrogenation transformation of an internal alkyne using [Cp*RuCl](4) as a precatalyst. The reaction shows regioselectivity and forms vinyl carbene complexes with various binding modes as intermediates. The access to spirocyclic and bridged ring systems through this reaction is of great significance in medicinal chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Joel Haefliger, Louise Ruyet, Nico Stuebke, Constantin G. Daniliuc, Ryan Gilmour
Summary: In this article, a cascade reaction is validated to generate novel gem-difluorinated isosteres from 1,3-diaryl cyclobutanols in a single operation, utilizing the biological significance of partially saturated, fluorine-containing rings and the physicochemical advantages conferred by fluorination.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Pu Chen, Zan Chen, Bi-Quan Xiong, Yun Liang, Ke-Wen Tang, Jun Xie, Yu Liu
Summary: A novel synthesis method is reported, involving visible-light-mediated reactions that enable the introduction of two different functional groups on carbon-carbon triple bonds in a tandem manner, leading to the successful preparation of the desired product.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Manas Mondal, Debajyoti Saha, Amit Saha
Summary: The synthesis of phenacyl-bis(dithiocarbamates) is achieved through a metal-free trifunctionalization reaction of phenylacetylene systems. This reaction involves oxidative bromination of phenyl acetylene followed by nucleophilic substitution with freshly prepared dithiocarbamate salt. Various gem-bis(dithiocarbamates) are prepared using different secondary amines and phenylacetylene systems with different substituents.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Physical
Pan Gao, Liping Cui, Guodong Zhang, Feng Chen
Summary: A catalytic defluorosilylation method is developed, providing concise and modular synthetic routes for gem-difluoroallylsilanes. Trifluoromethylalkenes and silacarboxylic acids are used as easy-to-prepare and stable silyl radical precursors. This method utilizes photoredox catalysis and features a unique decarboxylation followed by defluorosilylation without extra hydrogen atom transfer catalysis, offering mild reaction conditions and a broad substrate scope applicable to diverse electron-rich and electron-poor groups.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Organic
Guodong Li, Ke Yu, Jiajun Yang, Bo Xu, Qianjin Chen
Summary: An electrochemical radical strategy involving alkene substrates provides a powerful approach for alkene functionalization. The reaction described in the study enables the synthesis of gem-bisarylthio enamines with good functional group tolerance and high yields, without the need for additional oxidants, transition-metal catalysts, or bases, and can be easily scaled up for gram-scale production.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Applied
Ricardo J. Maza, Jorge J. Carbo, Elena Fernandez
Summary: The stability of alpha-Monoboryl anions and their resonance form borata-alkene systems are discussed in this review, along with the synthetic approaches and properties of the C=B bond. The characterization by X-ray diffraction and NMR data provide evidence for the partial boron-carbon double bond character, while reactivity studies demonstrate the nucleophilic potential of the C=B bond in electrophilic trapping examples. Homologation protocols with diborylmethane offer a facile method for introducing C(sp(3))-B bonds for subsequent transformations into functionalized products.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Editorial Material
Chemistry, Applied
Elena Fernandez
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Inorganic & Nuclear
Macarena Corro, Oriol Salvado, Sara Gonzalez, Paula Dominguez-Molano, Elena Fernandez
Summary: The renaissance in the application of gem-diborylalkanes since 2010 has led to new synthetic applications towards C-C and C-N bond formation. Activation of gem-diborylalkanes by Cu(I) catalysts generates active borylalky copper(I) species, allowing efficient trapping of several electrophilic reagents. Furthermore, modification of Cu(I) complexes with chiral ligands induces asymmetric platforms for the synthesis of enantioenriched organoboron compounds.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yao Liu, Raimon Puig de la Bellacasa, Bo Li, Ana Belen Cuenca, Shih-Yuan Liu
Summary: The first alpha-boryl diazo compound capable of engaging in classic synthetic organic diazo reaction chemistry, diazomethyl-1,2-azaborine 1, exhibits a wide range of reactivity, making it an exceptionally versatile synthetic building block for the 1,2-azaborine heterocyclic motif.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Jana Sendra, Efraim Reyes, Liher Prieto, Elena Fernandez, Jose L. Vicario
Summary: Hydrazones derived from cycloalkenones undergo an enantioselective transannular formal (3 + 2) cycloaddition catalyzed by a chiral phosphoric acid, providing high yields and excellent stereocontrol in the formation of complex adducts. These adducts can be converted into versatile stereodefined decalin- or octahydro-1H-indene-derived 1,3-diamines through simple reductive N-N cleavage.
Article
Chemistry, Applied
Sara Gonzalez, Oriol Salvado, Elena Fernandez
Summary: This article describes the conjugate addition of tert-butyllithium to vinyl systems of boronic esters to generate a borata-alkene intermediate, followed by a sequential S(N)2 reaction with alkyl halides, at room temperature. The reaction retains all the carbon atoms from the three starting materials involved in the assembly.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Mireia Pujol, Ricardo J. Maza, Oriol Salvado, Jorge J. Carbo, Elena Fernandez
Summary: This article describes the transformation of 1,1-diborylalkenes into (Z)-skipped dienes through Cu-I-phosphine catalyzed allylic coupling reactions. The preferential formation of (Z)-alpha-borylalkenyl copper (I) species and the subsequent nucleophilic attack explain the stereoselective nucleophilic substitution with allyl bromides. The eventual treatment of (Z)-skipped dienes with (NaOBu)-Bu-t promotes cyclization/aromatization patterns via enyne intermediates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Oriol Salvado, Paula Dominguez-Molano, Elena Fernandez
Summary: Palladium catalysis enables the cyclopropanation of 2-substituted 1,1-diborylalkenes with (trimethylsilyl)diazomethane, controlling the relative stereoselectivity. Furthermore, further reactions involving chiral boryl motifs lead to the formation of polyfunctional cycloopropyl alcohols with controlled enantioselectivity.
Article
Chemistry, Multidisciplinary
Raul Cosialls, Cristina Simo, Salvador Borros, Vanessa Gomez-Vallejo, Claudia Schmidt, Jordi Llop, Ana B. Cuenca, Angela Casini
Summary: In this study, the synthesis of F-18-labelled[Pd2L4](4+) metallacages was reported for the advancement of self-assembled metallosupramolecular architectures as new generation theranostic agents. Various spectroscopic and bio-analytical methods supported the formation of the host-guest cage-cisplatin complex. The biodistribution profiles of one of the cages, either alone or encapsulating cisplatin, were studied using PET/CT imaging in healthy mice in vivo, in combination with ICP-MS ex vivo.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Sara Gonzalez, Elena Fernandez
Summary: In this study, the carbolithiation reaction was employed to generate alpha-phenylboryl carbanions, which then reacted with carbonyl compounds through a boron-Wittig sequence.
Article
Chemistry, Applied
Jana Sendra, Oriol Salvado, Manuel Pedron, Efraim Reyes, Tomas Tejero, Elena Fernandez, Pedro Merino, Jose L. Vicario
Summary: The ability of cyclooctatetraene oxide to undergo ring contraction events under mild conditions using Bronsted acid catalysis has been investigated. Selectivity was found to be controlled by catalyst acidity and temperature, leading to either cycloheptatriene carbaldehyde or phenylacetaldehyde products. A mechanistic understanding of the reaction and the influence of the catalyst has been provided through experimental and computational data. Moreover, the acid-catalyzed ring contraction has been combined with in situ enantioselective allylation reaction, resulting in enantioenriched cycloheptatrienyl-substituted homoallylic alcohols. These alcohols have further been converted to enantioenriched oxaborinanes through copper-catalyzed nucleophilic borylation/cyclization protocol.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Paula Dominguez-Molano, Rosemary Weeks, Ricardo J. Maza, Jorge J. Carbo, Elena Fernandez
Summary: Regioselective borylcupration of borylated skipped (Z)-dienes generates diborylated alkylcopper species that undergo intramolecular stereospecific B/Cu1,3-rearrangement by migration of Bpin moiety from C(sp(2)) to C(sp(3)). DFT mechanistic studies reveal that boryl migration occurs through the formation of a 4-membered boracycle intermediate with a moderate free-energy barrier. Additionally, the use of KOMe forms stable Lewis base adducts with Bpin moieties, blocking the reaction. Following the 1,3-boron shift, in situ electrophilic trapping enables selective C-H, C-C, and C-X bond formations, leading to cyclic functionalized alkylidenecyclohexanes or alkylidenecyclobutanes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Paula Dominguez-Molano, Gerard Bru, Oriol Salvado, Ricardo J. Maza, Jorge J. Carbo, Elena Fernandez
Summary: The exchange of boryl moieties between alkenylboranes and diboron reagents is proposed as a stereospecific cross-metathesis pathway, leading to the formation of mixed diboron reagents. Density functional theory calculations suggest a mechanism for stereocontrolled C(sp(2))-B/B'-B' cross-metathesis with both symmetric and non-symmetric diboron reagents.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Wei W. Chen, Nahiane Pipaon Fernandez, Marta Diaz Baranda, Anton Cunillera, Laura G. Rodriguez, Alexandr Shafir, Ana B. Cuenca
Summary: This report discusses the stepwise construction of multi-substituted C(sp)TJ0VL(3)X carbon centers using gem-alpha,alpha-dimetalloid-substituted benzylic reagents. Highly chemoselective transformations of C-Si (or C-Sn) or C-B bonds in gem-C-sp(3) centers were achieved through various approaches, including metal-free arylation guided by iodanes and Suzuki-Miyaura arylation. DFT calculations show that the transfer of (alpha-Bpin)benzyl group proceeds via an unusual [5,5]-sigmatropic rearrangement driven by high-energy iodine(iii) center.
Review
Chemistry, Multidisciplinary
Ana B. Cuenca, Elena Fernandez
Summary: The boron-Wittig reaction involves the condensation of easy manageable lithium alpha-bis(boryl)carbanions with carbonyl derivatives to form metalloid-substituted alkenes, which are important building blocks for the synthesis of all-carbon substituted olefins. This reaction is stereoselective and can be applied to a variety of carbonyl derivatives, with a focus on controlling the stereochemical outcome. Its synthetic potential is demonstrated through applications to target compounds via subsequent C-C bond forming processes.
CHEMICAL SOCIETY REVIEWS
(2021)
