Article
Chemistry, Organic
Jing Liu, Baohui Zhang, Junjie Hu, Zhenpeng Qiu, Xinyan Chen, Xianxiang Tian, Qi Wang, Guohua Zheng, Ming Yuan
Summary: Here, we present an Ag+/S2O82--induced method for the synthesis of functionalized succinyl diamides with an all-carbon quaternary stereocenter via a radical aminoformylation/aryl-migration/desulfonylation cascade. This improved process utilizes oxalic monoamide, which is readily available and inexpensive, as a carbamoyl radical precursor through radical Smiles rearrangement. Additionally, the practical value of this synthesis strategy is enhanced by its tolerance to oxygen and water, operational simplicity, convenient reagents, and scalability.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Joshua A. Malone, Satish Chandra Philkhana, Jacob R. Stepherson, Fatimat O. Badmus, Frank R. Fronczek, Rendy Kartika
Summary: This article describes a new synthetic reaction that can generate all-carbon bisquaternary centers at the opposing side of alpha-carbons in cyclohexanone with four different substituents in a controlled manner.
Article
Chemistry, Organic
Yan-Li Xu, Zhou-Zhou Qin, Yu-Xia Wang, Peng-Fei Zhao, Hong-Feng Li, Zhi-Hong Du, Chao-Shan Da
Summary: Highly enantiopure and bioactive delta-valerolactones and pyrazolones, bearing alpha-all-carbon quaternary stereocentres, were successfully synthesized via a one-pot procedure using a new chiral squaramide catalyst. This method is economically efficient and environmentally benign, starting from readily available, inexpensive materials.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhaojiang Shi, Yuanyuan Li, Nan Li, Wei-Zhen Wang, Hao-Kuan Lu, Hong Yan, Yaofeng Yuan, Jun Zhu, Ke-Yin Ye
Summary: This study reports a facile electrochemical migratory cyclization of N-acylsulfonamides for the synthesis of a diverse array of benzoxathiazine dioxides. The inclusion of electrochemistry is crucial for realizing this novel transformation, as confirmed by both experiments and density-functional-theory calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Dong -Kai Wang, Liu-Bin Li, Fa-Liang Liu, Hui Qiu, Jiao-Zhe Li, Jianfeng Zhang, Chao Deng, Wen-Ting Wei
Summary: This study presents a novel method for the construction of all-carbon quaternary centers, specifically those with an alkyne-substituted framework, using a Fe-catalyzed formal insertion of diazo compounds into C(sp)-C(sp(3)) bonds of propargyl alcohols under mild conditions.
ACS CENTRAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Jeff K. Kerkovius, Alice R. Wong, Victor W. Mak, Sarah E. Reisman
Summary: The formation of quaternary stereogenic centers in polycyclic systems is achieved via a strategy based on the semi-pinacol reaction. Two fragments of similar size and complexity are joined by alkenyl lithium addition to an epoxy ketone, followed by a semi-pinacol rearrangement. Polycyclic scaffolds with quaternary stereogenic centers are generated in high yields, tolerating various functional groups. This method provides a useful strategy for the synthesis of complex polycyclic natural product-like scaffolds.
Article
Chemistry, Multidisciplinary
Mandeep S. Dhak, Dhanarajan Arunprasath, Stephen P. Argent, James D. Cuthbertson
Summary: This article describes a photoredox-mediated radical amidation ring-expansion sequence that allows the generation of all-carbon quaternary centers with a protected aminomethyl substituent. The methodology can be applied to both styrene and unactivated alkene substrates, resulting in the concise synthesis of structurally diverse sp(3)-rich amine derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Jian-Qiang Chen, Qi Chen, Baofu Chen, Jie Wu
Summary: A direct photoredox catalyzed radical-triggered tandem cyclization of 1,7-enynes with alkyloxalyl chlorides is developed, enabling the preparation of dihydropyranones containing all-carbon quaternary centers through alkoxycarbonylation/6-exo-dig cyclization/6-endo-trig cyclization with 1,7-enynes under mild conditions. Importantly, this approach provides a new route to polysubstituted dihydropyranones.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Sifan Li, Yu Wang, Zibo Wu, Weiliang Shi, Yibo Lei, Paul W. Davies, Wei Shu
Summary: A radical triggered fragmentary cyclization cascade reaction is proposed to provide rapid access into [1,2]-annulated indoles. The mechanism involves radical addition, cyclization, aryl migration, and C-N bond cyclization sequence.
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)
Article
Chemistry, Multidisciplinary
Su-Lei Zhang, Wen-Wen Zhang, Bi-Jie Li
Summary: In this study, a substrate-directed, iridium-catalyzed enantioselective hydroalkynylation was developed to construct an acyclic all-carbon quaternary stereocenter beta to a nitrogen atom. Experimental and computational studies were combined to reveal the mechanism and origin of regio- and enantioselectivities.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Zong-Wang Qiu, Liang Long, Zhi-Qiang Zhu, Hong-Fu Liu, Han-Peng Pan, Ai-Jun Ma, Jin-Bao Peng, Yong-Heng Wang, Hao Gao, Xiang-Zhi Zhang
Summary: This study reports an efficient metal-free method for constructing acyclic all-carbon quaternary stereocenters. The asymmetric catalytic visible-light-induced Paterno-Buchi cycloaddition/electrocyclic ring-opening/alpha-selective arylation reactions of alpha,beta-unsaturated carbonyl compounds were successfully achieved via a well-designed reaction cascade. The method is applicable to a wide range of compounds and provides access to synthetically useful building blocks.
Article
Chemistry, Multidisciplinary
Zexian Li, Minyan Wang, Zhuangzhi Shi
Summary: An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed, generating valuable multisubstituted perfluoroalkylated compounds in a single step. Mechanistically, photoinduced alkyl radical addition to an alkene leads to migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center, followed by generation of a C-radical bearing two electron-withdrawing groups and reduction by a hydrogen donor to complete the domino sequence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Niklas Radhoff, Armido Studer
Summary: The authors report a method for the preparation of bulky alpha-quaternary amides via a polar-radical crossover enolate oxidation-aryl migration cascade. The method is simple, efficient and scalable, and allows for the synthesis of alpha-quaternary amides in good to excellent yields. The reaction exhibits excellent functional group tolerance and can be applied to a wide range of substrates.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yihuo Liu, Siyu Ding, Mingli Xu, Jinli Xu, Dongping Cheng, Hong Wang, Xiaoliang Xu
Summary: A visible-light-promoted radical tandem reaction of N-arylsulfonyl-acrylamides with alpha-oxocarboxylic acids is reported, which undergoes decarboxylation, Smiles rearrangement, and intramolecular cyclization to afford a series of arylacylated oxindoles with potential pharmacological activities.
Article
Chemistry, Multidisciplinary
Sergio Cuesta-Galisteo, Johannes Schorgenhumer, Xiaofeng Wei, Estibaliz Merino, Cristina Nevado
Summary: This study presents a nickel-catalyzed asymmetric reductive hydroarylation method for synthesizing enantioenriched alpha-arylbenzamides. By using a BIm ligand, diethoxymethylsilane, and aryl halides, aryl groups can be selectively introduced to the internal position of the olefin, creating a new stereogenic center alpha to the N atom with neutral reagents and mild reaction conditions. This provides a straightforward route to pharmacologically relevant motifs found in anticancer drugs, SARS-CoV PLpro inhibitors, and KCNQ channel openers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Alexandre Genoux, Michal Biedrzycki, Estibaliz Merino, Eva Rivera-Chao, Anthony Linden, Cristina Nevado
Summary: A new family of cationic, bidentate gold(III) fluoride complexes have been prepared and characterized, showing reactivity with cyano and acetylene nucleophiles. The resulting arylgold(III)C(sp) complexes exhibit higher rates of C(sp(2))-C(sp) bond formation compared to phosphine-based monodentate systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Ana Milian, Manuel A. Fernandez-Rodriguez, Estibaliz Merino, Juan J. Vaquero, Patricia Garcia-Garcia
Summary: Metal-free borylative cyclization of biphenyl-embedded 1,3,5-trien-7-ynes in the presence of BCl3 provides synthetically useful borylated building blocks. The reaction temperature controls the formation of different borylated products. A proposed mechanism involving uncommon skeletal rearrangement is supported by DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Francisco Garnes-Portoles, Estibaliz Merino, Antonio Leyva-Perez
Summary: The synthesis of macrocycles, which are cyclized organic compounds with more than ten atoms, has traditionally been limited by the need for reversible reactions under highly diluted conditions to prevent the formation of intermolecular products. However, researchers have now demonstrated that the intramolecular Mizoroki-Heck reaction of ω-iodide cinnamates can proceed at higher concentrations (1 M) when catalyzed by few-atom Pd clusters, yielding different macrocycles in good yields. This paradigm shift allows for increased macrocycle production and the use of solid catalysts in flow reactions.
Article
Chemistry, Organic
Mercedes Zurro, Sergio Torres-Oya, Guillermo G. G. Otarola, Juan Jose Vaquero, Estibaliz Merino
Summary: A one-step chlorosulfonylation of acrylamides via a photo-catalytic redox process is reported, which provides α-chlorosulfonylamides with a quaternary center in high regioselectivity through radical process. This method is applicable to a broad range of substrates and affords the products in moderate to good yields.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Mercedes Zurro, Sergio Torres-Oya, Estibaliz Merino
Summary: This study describes a one-step synthesis of the anticancer drug bicalutamide from N-arylacrylamide using visible light. The approach involves a photocatalytic redox process, specifically a one-pot hydroxysulfonylation reaction. By using Na2Eosin Y as a photocatalyst and blue light, a variety of α-hydroxysulfonylamides with a quaternary center can be obtained with complete regioselectivity via a radical process, achieving moderate to good yields.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Francisco Maqueda-Zelaya, Jose Luis Acena, Estibaliz Merino, Juan J. Vaquero, David Sucunza
Summary: An efficient methodology has been developed for the synthesis of 4-alkoxy- and 4-aryloxybenzo[d][1,2,3]triazines via an intramolecular heterocyclization of 1-azido-2-[isocyano(p-tosyl)methyl]benzenes under basic conditions. DFT calculations were performed to gain a better understanding of the mechanism behind this heterocyclization, which demonstrated good to excellent yields with a broad scope.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Julia Altarejos, Estibaliz Merino, David Sucunza, Juan J. J. Vaquero, Javier Carreras
Summary: A facile one-pot (3 + 2) cycloaddition-isomerization-oxidation sequence using 2,2,2-trifluorodiazoethane and styryl derivatives has been developed for the synthesis of 5-aryl-3-trifluoromethylpyrazoles. The reaction showed broad functional group tolerance and high yields under mild conditions. DFT calculations confirmed the reactivity observed experimentally by analyzing the transition state energies of the cycloaddition reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Sara Senorans, Isabel Valencia, Estibaliz Merino, Marta Iglesias, Manuel A. Fernandez-Rodriguez, Eva M. Maya
Summary: The first example of a porous polymer containing B-N covalent bonds prepared using the solvent knitting strategy is reported. The polymer exhibits micromeso porosity, high thermal stability, and potential properties as a highly stable and efficient photocatalyst. After the first run, the catalyst improves its photocatalytic activity and maintains this activity in successive runs, making it a new type of material with potential applications.
Article
Chemistry, Organic
M. Soledad Garre, Guillermo G. Otarola, Estibaliz Merino, David Sucunza, Enrique Aguilar, M. Teresa Quiros, Juan J. Vaquero, Patricia Garcia-Garcia
Summary: Cyclobutane-fused dihydropyridones can be synthesized efficiently via a completely endo-selective gold-catalyzed cyclization of alkynylcyclobutanes with an appended amide, under mild conditions. The observed selectivity, opposite to that observed for the cyclization of related alcohols and acids, is supported by DFT calculations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Engineering, Environmental
Noemi Salardon, Guillermo Otarola, Clara Manas, Estibaliz Merino, Belen Batanero
Summary: This study describes the efficient metal-free electrosynthesis of 2,4-dinitrophenyl iodide starting from 2,4-dinitrophenylhydrazine. Surprisingly, this method minimizes the formation of anodic multilayered film under the applied experimental conditions. The sustainable iodide-mediated oxidative dehydrazination enables the coupling reaction of electrogenerated iodine with aryl radicals from electron-deficient arylhydrazines using electricity as the driving force and an inexpensive halogen source.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Helene Beucher, Johannes Schoergenhumer, Estibaliz Merino, Cristina Nevado
Summary: A chelation-assisted oxidative addition of gold(I) into the C-C bond of biphenylene was achieved in this study. The presence of coordinating groups played a crucial role in the successful activation of strained C-C bonds by gold. This research provides a new and straightforward method for synthesizing cyclometalated gold(III) complexes.
