Article
Chemistry, Multidisciplinary
Song Zhang, Zhenghuai Feng, Chunhui Jiang, Xiaojun Yu, Jianke Pan, Juan Du, Zhiyu Jiang, Yuan Chen, Tianli Wang
Summary: In this study, a series of chiral epsilon-benzosultams bearing phosphorus functionalities were synthesized successfully. Control experiments were conducted to elucidate the plausible reaction mechanism of this chemical transformation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Organic
Yi-Ren Zhu, Jie Xu, Hui-Fang Jiang, Rui-Jing Fang, Yan-Jun Zhang, Lu Chen, Chen Sun, Fei Xiong
Summary: This article reviews the application of bifunctional sulfonamide as a hydrogen-bonding catalyst in asymmetric organocatalysis after 2011, highlighting asymmetric processes such as aldol reaction, Michael addition, Mannich reaction, desymmetrization, and cyclization.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xiangpei Chai, Xinheng Hu, Xiaowei Zhao, Yanli Yin, Shanshan Cao, Zhiyong Jiang
Summary: This research reports a radical-based manifold that achieves highly enantioselective transformations of N-arylglycines. The dual catalytic system involving a chiral phosphoric acid and a photoredox sensitizer offers a new approach for the synthesis of valuable organic compounds with satisfactory results and high enantiocontrol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Yasushi Yoshida, Takashi Mino, Masami Sakamoto
Summary: This study reports the design and development of chiral cyclic diarylbromonium salts, enabling highly selective Lewis acid XB catalysis with products reaching up to 96% ee.
Article
Biochemistry & Molecular Biology
Yasushi Yoshida, Tatsuya Ao, Takashi Mino, Masami Sakamoto
Summary: In this study, chiral halonium salts with an N-nitrosamine moiety were developed and applied to the Mannich reaction. The novel bromonium salt catalyst showed high yields and up to 80% ee. This is the first catalytic application of N-nitrosamines.
Article
Engineering, Environmental
Anton De Vylder, Jeroen Lauwaert, Maarten K. Sabbe, Marie-Francoise Reyniers, Jeriffa De Clercq, Pascal Van Der Voort, Joris W. Thybaut
Summary: The effects of water and silanol groups on the liquid-phase amine-catalyzed aldol reaction of acetone with 4-nitrobenzaldehyde have been elucidated with a comprehensive theoretical model. Water and silanol groups were found to reduce Gibbs free energy barriers for certain reaction steps, resulting in overall lower barriers and more efficient reactions. The effect of water was more pronounced in apolar hexane compared to DMSO, leading to less deactivation of the amine and lower barriers for reactions where water assists in the transition state.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Organic
Alex Marti, Marc Montesinos-Magraner, Antonio M. Echavarren, Allegra Franchino
Summary: In this article, the application of H-bonded counterion-directed catalysis to the Au(I)-catalyzed enantioselective tandem cycloisomerization-addition reaction of 2-alkynyl enones was presented. Bicyclic furans were obtained in moderate to excellent yield and enantioselectivity using the optimal catalytic system selected through high-throughput screening. A significant enantioselectivity switch was observed upon addition of the achiral Au(I) component to the Ag(I) salt.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Felix Feige, Jeen Al-Issa, Julius F. Kogel, Enno Lork, Elena Rychagova, Sergey Ketkov, Jens Beckmann
Summary: The reaction between sodium salts of perfluorinated tertiary alcohols and SiCl4 resulted in the formation of di-substituted dichlorosilanes and corresponding silanediols, which are stable towards self-condensation at ambient conditions. Similar compounds, disiloxanes, were also prepared in a similar manner.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Stuart C. D. Kennington, Saul F. Teloxa, Miguel Mellado-Hidalgo, Oriol Galeote, Sabrina Puddu, Marina Bellido, Pedro Romea, Felix Urpi, Gabriel Aullon, Merce Font-Bardia
Summary: A direct and asymmetric aldol reaction of N-acyl thiazinanethiones with aromatic aldehydes catalyzed by chiral nickel(II) complexes was reported. The reaction gives high yields of O-TIPS-protected anti-aldol adducts with remarkable stereocontrol and atom economy. The removal of the achiral scaffold provides enantiomerically pure intermediates with synthetic interest for producing anti-alpha-amino-beta-hydroxy and alpha,beta-dihydroxy carboxylic derivatives, with theoretical calculations explaining the observed high stereocontrol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Ming Zhang, Xiao-Chen Wang
Summary: This method presents a mild and efficient approach for synthesizing enantioenriched tetrahydroquinoline-fused cyclobutenes through a cascade reaction, catalyzed by chiral spiro-bicyclic bisboranes. The bisboranes function by catalyzing hydride transfer and activating the alkynone substrate for an enantioselective cycloaddition reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Yasushi Yoshida, Tappei Fujimura, Takashi Mino, Masami Sakamotoa
Summary: This study reports an asymmetric synthesis method of chiral N,S-acetals using a chiral iodonium salt catalyst under neutral conditions, with good-to-excellent yields and enantioselectivities. The reaction mechanism and catalyst activation were studied through NMR experiments and DFT calculations, and the abnormal counteranion effect was also investigated.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Jacqkis Davis, Mojgan Gharaee, Chamini Karunaratne, Jose Cortes Vazquez, Mikayla Haynes, Weiwei Luo, Vladimir N. Nesterov, Thomas Cundari, Hong Wang
Summary: Cooperative enamine-metal Lewis acid catalysis is a powerful method for constructing carbon-carbon and carbon-heteroatom bonds. A concise synthetic method for asymmetric synthesis of chromans has been developed, yielding tricyclic chromans with three consecutive stereogenic centers in high yields and stereoselectivity. It is believed that the strong activation of salicylaldehydes through chelation to the metal Lewis acid and the bifunctional nature of the catalyst contribute to the high yields and enantioselectivity of the reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Zhenghuai Feng, Hongkui Zhang, Xiaoyu Ren, Chunhui Jiang, Guowei Gao, Tianli Wang
Summary: This study demonstrates asymmetric hydrophosphonylation of carbonyl compounds using thiourea-derived bifunctional phosphonium salt catalysis, resulting in high yields and excellent enantioselectivities. Mechanistic results suggest the importance of ion pair and hydrogen-bonding interactions in asymmetric induction.
Article
Chemistry, Multidisciplinary
Naoto Sato, Yoshiyuki Kuroda, Hiroaki Wada, Atsushi Shimojima, Kazuyuki Kuroda
Summary: Cage siloxanes modified with diisopropylsilanol groups were synthesized and crystallized into a layered structure containing 1,3,5-trimethylbenzene molecules in the interlayer voids, indicating the crucial role of organic groups attached to the silanol groups in the assembling behavior of cage siloxanes.
Article
Chemistry, Multidisciplinary
Teng Yuan, Kelton Radefeld, Chuan Shan, Carter Wegner, Erin Nichols, Xiaohan Ye, Qi Tang, Lukasz Wojtas, Xiaodong Shi
Summary: Here, we have reported an intermolecular asymmetric hydrative aldol reaction by using a vinyl-gold intermediate under ambient conditions. This reaction provides a base-free approach to β-hydroxy amides with high efficiency, yielding up to 95% and with over 50 examples. The use of vinyl gold intermediate as a reactive nucleophile and Fe(acac)(3) as a critical co-catalyst prevents undesired protodeauration, allowing the transformation to proceed under mild conditions with excellent functional group tolerance and stereoselectivity (>20:1 d.r. and up to 99% ee).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Allan He, Zihao Shen, Haozhe Wang, Weiwei Xie, Zhen Wang, Luis Garay, James C. Fettinger, Raphael P. Hermann, Yimei Zhu, Valentin Taufour, Susan M. Kauzlarich
Summary: The new Eu(5)Al(3)Sh(6) phase has been synthesized as a pure phase with large, high-quality crystals using Sn flux methods. The structure features disordered Al clusters in the form of dual tetrahedra and exhibits unique electronic properties. Evaluation of its properties includes magnetic behavior, oxidation states, and electronic structure calculations.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Wenxing Zou, James C. Fettinger, Petra Vasko, Philip P. Power
Summary: A series of heteroleptic aryl copper(I) thiolato complexes were synthesized and characterized, with some complexes exhibiting unconventional structural arrangements. The structural features and reactivity of the complexes are influenced by the aryl groups present.
Article
Chemistry, Physical
Nicolas R. Ball-Jones, Angel A. Cobo, Brittany M. Armstrong, Benjamin Wigman, James C. Fettinger, Jason E. Hein, Annaliese K. Franz
Summary: A mechanism for scandium-catalyzed asymmetric allylsilane annulation reaction is proposed and supported by experimental evidence. The study reveals the effects of catalyst solubility, coordination sequence, and timing of nucleophile addition on the reaction rate. Ligand-dependent acceleration of the catalysis is observed.
Article
Chemistry, Inorganic & Nuclear
Ting Yi Lai, James C. Fettinger, Philip P. Power
Summary: In this study, the reaction of diarylgermylene Ge(Ar-Me6)(2) with azobenzene was investigated, and the resulting products were characterized using spectroscopy and X-ray crystallography.
Article
Chemistry, Multidisciplinary
Fatat B. El Dhaibi, Ali Youssef, James C. Fettinger, Mark J. Kurth, Makhluf J. Haddadin
Summary: A new approach to synthesize a series of 1,2,4-[e]-benzotriazine and cinnoline derivatives from 3-substituted isoindolin-1-one is reported in this study. The reported products are obtained through an economical two-step synthetic procedure with fair-to-high yields. The transformation involves intramolecular cyclization of the corresponding 3-substituted isoindolin-1-ones and an addition reaction from 2-cyanobenzaldehyde or 2-nitroaniline derivatives.
Article
Chemistry, Multidisciplinary
Yannick Kraemer, Clement Ghiazza, Abbey N. Ragan, Shengyang Ni, Sigrid Lutz, Elizabeth K. Neumann, James C. Fettinger, Nils Noethling, Richard Goddard, Josep Cornella, Cody Ross Pitts
Summary: By leveraging the accessibility of SF5Cl and Ar-SF4Cl compounds, we combined the chemistry of SF5 and SF4Ar groups with strain-release functionalization to synthesize structurally unique bicyclopentanes bearing distinct bioisosterism elements. These previously unknown structures not only expand the options for highly desired three-dimensional fluorinated building blocks but also provide insights into a more general effect observed in bicyclopentanes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Ashlee K. Hauble, Caitlin M. Crawford, Jesse M. Adamczyk, Maxwell Wood, James C. Fettinger, Eric S. Toberer, Susan M. Kauzlarich
Summary: Layered Zintl phases with A2MPn2 stoichiometry are potential thermoelectric materials with complex chemistry. This study focuses on Yb2-xEuxCdSb2 solid solution and investigates the impact of defects on thermal and electronic properties. The research reveals that tuning the defect structure can significantly improve the thermoelectric performance.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Organic
Benjamin D. Bergstrom, Garrett Toth-Williams, Anna Lo, Jeffrey W. Toman, James. C. Fettinger, Jared T. Shaw
Summary: Polysubstituted allenes are valuable synthetic intermediates that offer structural complexity, modularity, and chirality for further transformations. In this study, a novel method for synthesizing tetrasubstituted allenes with geminal acyl/alkoxy substitution is reported. These unique push-pull allenes demonstrate bench-stability and interesting reactivity in various applications.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Lilia M. Baldauf, James C. Fettinger, Marilyn M. Olmstead, Kamran B. Ghiassi, Alan L. Balch
Summary: Two new cocrystals, named 1 and 2, were discovered with a clamshell arrangement of two porphyrins surrounding a central C70 molecule. Cocrystal 1 has a unique double-clamshell arrangement, while cocrystal 2 has a simple clamshell arrangement.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Rongqing Shang, Allan He, Elizabeth L. Kunz Wille, Na Hyun Jo, James C. Fettinger, Paul C. Canfield, Susan M. Kauzlarich
Summary: The solid solutions of Yb14ZnSb11 with different RE3+ elements were prepared to investigate the intermediate valency of Yb in Yb14ZnSb11. The substitution of Yb with RE3+ elements can impact the valency of Yb ions. Large crystals were grown using Sn-flux, the structure and magnetic susceptibility were studied. The results showed that all compounds crystallize in the Ca14AlSb11 structure type and the RE3+ ions exhibit a size-dependent preference for substitution at the Yb site.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Connor P. McLoughlin, James C. Fettinger, Philip P. Power
Summary: Six new transition-metal aryloxides were synthesized and characterized to compare the steric and dispersive characteristics of their substituents. The results show that the -C6H2-2,4,6-Cy-3 substituent has higher dispersive energy donor properties and influences the thermal stability. Complexes 1 and 2 exhibit high thermal stability and short-contact H···H interactions, while complexes 5 and 6 have a lower association number due to the lower dispersion energy donor properties of the -OC6H3-2,6-Pr-i (2) ligand.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Alice C. Phung, James C. Fettinger, Philip P. Power
Summary: A series of ferriostannylenes with different iron and/or tin substituents were synthesized and their structures and spectroscopic properties were investigated. The results showed that the substituents have significant effects on the structure and properties of the compounds.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Leo W. T. Parsons, James C. C. Fettinger, Louise A. A. Berben
Summary: This study explores N-alkylation and N-metallation of pyridine to understand how metal-ligand complexes can mimic NAD(+) redox chemistry. The syntheses of substituted dipyrazolylpyridine (pz(2)P) compounds (pz(2)P)Me+ (1(+)) and (pz(2)P)GaCl2+ (2(+)) are reported and compared with previous transition element pz(2)P complexes. Cyclic voltammetry measurements show that cationic 1(+) and 2(+) exhibit irreversible reduction events at an anodic potential of SIM;900 mV, unlike the neutral pz(2)P complexes of divalent metals.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Mingchun Gao, Jose M. Ruiz, Emily Jimenez, Anna Lo, Croix J. Laconsay, James C. Fettinger, Dean J. Tantillo, Jared T. Shaw
Summary: Substrates designed for 1,4-C-H insertion to produce benzocyclobutenes underwent a unique elimination reaction, resulting in the formation of ortho-quinone dimethide (o-QDM) intermediates that further participated in Diels-Alder or hetero-Diels-Alder cycloadditions. The analogous benzylic acetals or ethers, on the other hand, bypassed the C-H insertion pathway and, after hydride transfer, underwent a de-aromatizing elimination reaction to form o-QDM at ambient temperature. The resulting dienes exhibited high diastereo- and regio-selectivity when involved in various cycloaddition reactions. This method represents a rare example of catalytic o-QDM generation without the involvement of a benzocyclobutene, and it offers a mild and ambient temperature approach to access these valuable intermediates. DFT calculations provided support for the proposed mechanism. Furthermore, this methodology was successfully applied to the synthesis of (+/-)-isolariciresinol with an overall yield of 41%.
Article
Chemistry, Multidisciplinary
Wenxing Zou, Kristian L. Mears, James C. Fettinger, Philip P. Power
Summary: Thermal Sn-C cleavage in diarylstannylene Sn(Ar-iPr4)(2) was used to generate radicals for alkyne arylstannylation. The reaction produced aryl vinyl stannylene complexes with different substituents and a known distannene.
CHEMICAL COMMUNICATIONS
(2023)
