6852-56-8Relevant academic research and scientific papers
Cobalt-Catalyzed Deoxygenative Hydroboration of Nitro Compounds and Applications to One-Pot Synthesis of Aldimines and Amides
Gudun, Kristina A.,Hayrapetyan, Davit,Khalimon, Andrey Y.,Segizbayev, Medet,Slamova, Ainur,Zakarina, Raikhan
, (2021/11/30)
The commercially available and bench-stable Co(acac)2 ligated with bis[(2-diphenylphosphino)phenyl] ether (dpephos) was employed for selective room temperature hydroboration of nitro compounds with HBPin (TOF up to 4615 h?1), tolerating halide, hydroxy, amino, ether, ester, lactone, amide and heteroaromatic functionalities. These reactions offered a direct access to a variety of N-borylamines RN(H)BPin, which were in situ treated with aldehydes and carboxylic acids to produce a series of aldimines and secondary carboxamides without the need for dehydrating and/or coupling reagents. Combination of these transformations in a sequential one-pot manner allowed for direct and selective synthesis of aldimines and secondary carboxamides from readily available and inexpensive nitro compounds.
Expanding Coefficient: A Parameter to Assess the Stability of Induced-Fit Complexes
Talotta, Carmen,Concilio, Gerardo,De Rosa, Margherita,Soriente, Annunziata,Gaeta, Carmine,Rescifina, Antonio,Ballester, Pablo,Neri, Placido
supporting information, p. 1804 - 1808 (2021/03/08)
Here we propose a new parameter, the Expanding Coefficient (EC), that can be correlated with the thermodynamic stability of supramolecular complexes governed by weak secondary interactions and obeying the induced-fit model. The EC values show a good linear relationship with the log Kapp of the respective pseudorotaxane complexes investigated. According to Cram's Principle of Preorganization, the EC can be considered an approximate mechanical measure of the host's reorganization energy cost upon adopting the final bound geometry.
Transient imine as a directing group for the metal-free o-C-H borylation of benzaldehydes
Rej, Supriya,Chatani, Naoto
supporting information, p. 2920 - 2929 (2021/03/01)
Organoboron reagents are important synthetic intermediates and have wide applications in synthetic organic chemistry. The selective borylation strategies that are currently in use largely rely on the use of transition-metal catalysts. Hence, identifying much milder conditions for transition-metal-free borylation would be highly desirable. We herein present a unified strategy for the selective C-H borylation of electron-deficient benzaldehyde derivatives using a simple metal-free approach, utilizing an imine transient directing group. The strategy covers a wide spectrum of reactions and (i) even highly sterically hindered C-H bonds can be borylated smoothly, (ii) despite the presence of other potential directing groups, the reaction selectively occurs at the o-C-H bond of the benzaldehyde moiety, and (iii) natural products appended to benzaldehyde derivatives can also give the appropriate borylated products. Moreover, the efficacy of the protocol was confirmed by the fact that the reaction proceeds even in the presence of a series of external impurities.
Trimethyl Borate-Catalyzed, Solvent-Free Reductive Amination
Ramachandran, P. Veeraraghavan,Choudhary, Shivani,Singh, Aman
, p. 4274 - 4280 (2021/03/09)
Solvent-free reductive amination of aldehydes and ketones with aliphatic and aromatic amines in high-to-excellent yields has been achieved with sub-stoichiometric trimethyl borate as promoter and ammonia borane as reductant.
2D sp2 Carbon-Conjugated Porphyrin Covalent Organic Framework for Cooperative Photocatalysis with TEMPO
Chen, Rufan,Hao, Huimin,Lang, Xianjun,Shi, Ji-Long,Wang, Cheng
supporting information, p. 9088 - 9093 (2020/03/30)
2D covalent organic frameworks (COFs) are receiving ongoing attention in semiconductor photocatalysis. Herein, we present a photocatalytic selective chemical transformation by combining sp2 carbon-conjugated porphyrin-based covalent organic framework (Por-sp2c-COF) photocatalysis with TEMPO catalysis illuminated by 623 nm red light-emitting diodes (LEDs). Highly selective conversion of amines into imines was swiftly afforded in minutes. Specifically, the π-conjugation of porphyrin linker leads to extensive absorption of red light; the sp2 ?C=C? double bonds linkage ensures the stability of Por-sp2c-COF under high concentrations of amine. Most importantly, we found that crystalline framework of Por-sp2c-COF is pivotal for cooperative photocatalysis with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). This work foreshadows that the outstanding hallmarks of COFs, particularly crystallinity, could be exploited to address energy and environmental challenges by cooperative photocatalysis.
A Carbazolyl Porphyrin-Based Conjugated Microporous Polymer for Metal-Free Photocatalytic Aerobic Oxidation Reactions
Jiang, Jun,Liang, Zhongxiu,Xiong, Xiaoyan,Zhou, Xiantai,Ji, Hongbing
, p. 3523 - 3529 (2020/05/25)
Herein, a carbazolyl porphyrin-based π-conjugated microporous polymer was prepared via simple FeCl3-catalyzed oxidative polymerization. The resulting polymer (TCPP-CMP) exhibits high surface area, permanent pores, good stability, broad light absorption range and suitable redox potentials. As expected, TCPP-CMP is a highly effective metal-free and heterogeneous photocatalyst for a variety of aerobic oxidation reactions, including oxidative coupling of primary amines, oxidative dehydrogenation of secondary amines, and oxidation of sulfides into sulfoxides using molecular oxygen under visible light irradiation. Importantly, natural sunlight is able to promote the aerobic oxidation of benzylamine and thioanisole via TCPP-CMP photocatalyst with high conversion and selectivity, which are comparable with reactions conducted under artificial light. In addition, heterogeneous TCPP-CMP has good recyclability, which retained its activity even after four cycles. The current work lays the foundation for future applications of TCPP-CMP as metal-free heterogeneous photocatalyst for aerobic oxidation reactions.
Cobalt-Catalyzed α-Arylation of Substituted α-Bromo α-Fluoro β-Lactams with Diaryl Zinc Reagents: Generalization to Functionalized Bromo Derivatives
Br?se, Stefan,Chen, Hi-Yung,Cossy, Janine,Koch, Vanessa,Lei, Aiwen,Lorion, Mélanie M.,Nieger, Martin
supporting information, p. 13163 - 13169 (2020/09/23)
A cobalt-catalyzed cross-coupling of α-bromo α-fluoro β-lactams with diarylzinc or diallylzinc reagents is herein disclosed. The protocol proved to be general, chemoselective and operationally simple allowing the C4 functionalization of β-lactams. The substrate scope was expanded to α-bromo lactams and amides, α-bromo lactones and esters as well as N- and O-containing heterocycles.
Ni-Catalyzed asymmetric reduction of α-keto-β-lactams: via DKR enabled by proton shuttling
Wang, Fangyuan,Tan, Xuefeng,Wu, Ting,Zheng, Long-Sheng,Chen, Gen-Qiang,Zhang, Xumu
supporting information, p. 15557 - 15560 (2020/12/30)
Chiral α-hydroxy-β-lactams are key fragments of many bioactive compounds and antibiotics, and the development of efficient synthetic methods for these compounds is of great value. The highly enantioselective dynamic kinetic resolution (DKR) of α-keto-β-lactams was realized via a novel proton shuttling strategy. A wide range of α-keto-β-lactams were reduced efficiently and enantioselectively by Ni-catalyzed asymmetric hydrogenation, providing the corresponding α-hydroxy-β-lactam derivatives with high yields and enantioselectivities (up to 92% yield, up to 94% ee). Deuterium-labelling experiments indicate that phenylphosphinic acid plays a pivotal role in the DKR of α-keto-β-lactams by promoting the enolization process. The synthetic potential of this protocol was demonstrated by its application in the synthesis of a key intermediate of Taxol and (+)-epi-Cytoxazone. This journal is
Chemoselective photocatalytic oxidation of alcohols to aldehydes and ketones by nitromethane on titanium dioxide under violet 400 nm LED light irradiation
Kaboudin, Babak,Kazemi, Foad,Rahimi Niaraki, Azam,Saraee, Mohammad Reza
, p. 2326 - 2330 (2020/04/03)
In this study, for the first time, nitroalkanes, especially nitromethane, have been used as electron acceptors for the highly chemoselective oxidation of alcohols in the presence of a TiO2 photocatalyst under 400 nm LED irradiation. The reactions showed excellent selectivity for the production of aldehydes. Interestingly, aldehydes such as benzaldehyde and p-methoxybenzaldehyde are stable under the reaction conditions. In the case of the use of 2-nitropropane and 2-methyl-2-nitropropane, the product imine, which is the result of the reaction of the aldehyde with aliphatic amine, is also obtained.
Single Atomically Anchored Cobalt on Carbon Quantum Dots as Efficient Photocatalysts for Visible Light-Promoted Oxidation Reactions
Wang, Qin,Li, Jin,Tu, Xianjun,Liu, Hongbo,Shu, Miao,Si, Rui,Ferguson, Calum T. J.,Zhang, Kai. A. I.,Li, Run
, p. 734 - 743 (2020/02/04)
Generation of efficient light-induced charge separation inside the photocatalyst is an essential factor for a high catalytic efficiency. The usual immobilization of metal or metal oxide particles on semiconductor photocatalysts offers an uncontrolled assembly of active sites during the reaction. The introduction of single metal atoms on photocatalysts can lead to extremely high atomic utilization and precise active sites. However, this approach is limited because of the lack of suitable photosensitizers for single atom immobilization. Here, we have designed photocatalytic carbon quantum dots with anchoring sites for single cobalt atoms in a defined Co-N4 structure via facile pyrolysis of vitamin B12. Carbon dots functioned as both light-harvesting antenna and support for the cobalt atom with high atom loadings up to 3.27 wt %. This new photocatalytic material demonstrated enhanced visible light absorption, efficient charge separation, and reduced electrochemical impedance, while single Co atoms acted as the active site with strong oxidative ability. As a result, the photocatalysts showed excellent visible light-promoted photocatalytic efficiency with oxygen evolution rates up to 168 μmol h-1 g-1 via water oxidation, imine formation with high conversion (～90%) and selectivity (>99%), and complete photodegradation of organic dyes.
