scholarly journals Difunctionalization of Alkenes and Alkynes via Intermolecular Radical and Nucleophilic Additions

Molecules ◽  
2020 ◽  
Vol 26 (1) ◽  
pp. 105
Author(s):  
Hongjun Yao ◽  
Wenfei Hu ◽  
Wei Zhang

Popular and readily available alkenes and alkynes are good substrates for the preparation of functionalized molecules through radical and/or ionic addition reactions. Difunctionalization is a topic of current interest due to its high efficiency, substrate versatility, and operational simplicity. Presented in this article are radical addition followed by oxidation and nucleophilic addition reactions for difunctionalization of alkenes or alkynes. The difunctionalization could be accomplished through 1,2-addition (vicinal) and 1,n-addition (distal or remote) if H-atom or group-transfer is involved in the reaction process. A wide range of moieties, such as alkyl (R), perfluoroalkyl (Rf), aryl (Ar), hydroxy (OH), alkoxy (OR), acetatic (O2CR), halogenic (X), amino (NR2), azido (N3), cyano (CN), as well as sulfur- and phosphorous-containing groups can be incorporated through the difunctionalization reactions. Radicals generated from peroxides or single electron transfer (SET) agents, under photoredox or electrochemical reactions are employed for the reactions.

2019 ◽  
Author(s):  
Michael Oschmann ◽  
Linus Johansson Holm ◽  
Oscar Verho

Benzofurans are everywhere in nature and they have been extensively studied by medicinal chemists over the years because of their chemotherapeutic and physiological properties. Herein, we describe a strategy that can be used to access elaborate benzo-2-carboxamide derivatives, which involves a synthetic sequence of 8-aminoquinoline directed C–H arylations followed by transamidations. For the directed C–H arylations, Pd catalysis was used to install a wide range of aryl and heteroaryl substituents at the C3 position of the benzofuran scaffold in high efficiency. Directing group cleavage and further diversification of the C3-arylated benzofuran products were then achieved in a single synthetic operation through the utilization of a two-step transamidation protocol. By bocylating the 8-aminoquinoline amide moiety of these products, it proved possible to activate them towards aminolysis with different amine nucleophiles. Interestingly, this aminolysis reaction was found to proceed efficiently without the need of any additional catalyst or additive. Given the high efficiency and modularity of this synthetic strategy, it constitute a very attractive approach for generating structurally-diverse collections of benzofuran derivatives for small molecule screening.


Author(s):  
S.V. Borshch ◽  
◽  
R.M. Vil’fand ◽  
D.B. Kiktev ◽  
V.M. Khan ◽  
...  

The paper presents the summary and results of long-term and multi-faceted experience of international scientific and technical cooperation of Hydrometeorological Center of Russia in the field of hydrometeorology and environmental monitoring within the framework of WMO programs, which indicates its high efficiency in performing a wide range of works at a high scientific and technical level. Keywords: World Meteorological Organization, major WMO programs, representatives of Hydrometeorological Center of Russia in WMO


Author(s):  
J. Schiffmann

Small scale turbomachines in domestic heat pumps reach high efficiency and provide oil-free solutions which improve heat-exchanger performance and offer major advantages in the design of advanced thermodynamic cycles. An appropriate turbocompressor for domestic air based heat pumps requires the ability to operate on a wide range of inlet pressure, pressure ratios and mass flows, confronting the designer with the necessity to compromise between range and efficiency. Further the design of small-scale direct driven turbomachines is a complex and interdisciplinary task. Textbook design procedures propose to split such systems into subcomponents and to design and optimize each element individually. This common procedure, however, tends to neglect the interactions between the different components leading to suboptimal solutions. The authors propose an approach based on the integrated philosophy for designing and optimizing gas bearing supported, direct driven turbocompressors for applications with challenging requirements with regards to operation range and efficiency. Using previously validated reduced order models for the different components an integrated model of the compressor is implemented and the optimum system found via multi-objective optimization. It is shown that compared to standard design procedure the integrated approach yields an increase of the seasonal compressor efficiency of more than 12 points. Further a design optimization based sensitivity analysis allows to investigate the influence of design constraints determined prior to optimization such as impeller surface roughness, rotor material and impeller force. A relaxation of these constrains yields additional room for improvement. Reduced impeller force improves efficiency due to a smaller thrust bearing mainly, whereas a lighter rotor material improves rotordynamic performance. A hydraulically smoother impeller surface improves the overall efficiency considerably by reducing aerodynamic losses. A combination of the relaxation of the 3 design constraints yields an additional improvement of 6 points compared to the original optimization process. The integrated design and optimization procedure implemented in the case of a complex design problem thus clearly shows its advantages compared to traditional design methods by allowing a truly exhaustive search for optimum solutions throughout the complete design space. It can be used for both design optimization and for design analysis.


2021 ◽  
Vol 11 (14) ◽  
pp. 6549
Author(s):  
Hui Liu ◽  
Ming Zeng ◽  
Xiang Niu ◽  
Hongyan Huang ◽  
Daren Yu

The microthruster is the crucial device of the drag-free attitude control system, essential for the space-borne gravitational wave detection mission. The cusped field thruster (also called the High Efficiency Multistage Plasma Thruster) becomes one of the candidate thrusters for the mission due to its low complexity and potential long life over a wide range of thrust. However, the prescribed minimum of thrust and thrust noise are considerable obstacles to downscaling works on cusped field thrusters. This article reviews the development of the low power cusped field thruster at the Harbin Institute of Technology since 2012, including the design of prototypes, experimental investigations and simulation studies. Progress has been made on the downscaling of cusped field thrusters, and a new concept of microwave discharge cusped field thruster has been introduced.


Synthesis ◽  
2020 ◽  
Author(s):  
Ikyon Kim ◽  
Sung June Kim ◽  
Sunhee Lee

AbstractBroadening of nitrogen-fused heteroaromatic chemical space such as indolizine and pyrrolo[1,2-a]pyrazine was achieved via FeCl­3-catalyzed nucleophilic addition of these N-fused aromatic compounds to a wide range of azolinium systems generated in situ, leading to novel N-fused heteroaromatic scaffolds with dearomatized N-heterocyclic substituents regioselectively. Nucleophilic addition of indolizines and pyrrolo[1,2-a]pyrazines mainly occurred at the C1 position of the isoquinoliniums and at the C4 site of the quinoliniums.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Alexander D. Taylor ◽  
Qing Sun ◽  
Katelyn P. Goetz ◽  
Qingzhi An ◽  
Tim Schramm ◽  
...  

AbstractDeposition of perovskite films by antisolvent engineering is a highly common method employed in perovskite photovoltaics research. Herein, we report on a general method that allows for the fabrication of highly efficient perovskite solar cells by any antisolvent via manipulation of the antisolvent application rate. Through detailed structural, compositional, and microstructural characterization of perovskite layers fabricated by 14 different antisolvents, we identify two key factors that influence the quality of the perovskite layer: the solubility of the organic precursors in the antisolvent and its miscibility with the host solvent(s) of the perovskite precursor solution, which combine to produce rate-dependent behavior during the antisolvent application step. Leveraging this, we produce devices with power conversion efficiencies (PCEs) that exceed 21% using a wide range of antisolvents. Moreover, we demonstrate that employing the optimal antisolvent application procedure allows for highly efficient solar cells to be fabricated from a broad range of precursor stoichiometries.


Energies ◽  
2021 ◽  
Vol 14 (3) ◽  
pp. 607
Author(s):  
Tommy R. Powell ◽  
James P. Szybist ◽  
Flavio Dal Forno Chuahy ◽  
Scott J. Curran ◽  
John Mengwasser ◽  
...  

Modern boosted spark-ignition (SI) engines and emerging advanced compression ignition (ACI) engines operate under conditions that deviate substantially from the conditions of conventional autoignition metrics, namely the research and motor octane numbers (RON and MON). The octane index (OI) is an emerging autoignition metric based on RON and MON which was developed to better describe fuel knock resistance over a broader range of engine conditions. Prior research at Oak Ridge National Laboratory (ORNL) identified that OI performs reasonably well under stoichiometric boosted conditions, but inconsistencies exist in the ability of OI to predict autoignition behavior under ACI strategies. Instead, the autoignition behavior under ACI operation was found to correlate more closely to fuel composition, suggesting fuel chemistry differences that are insensitive to the conditions of the RON and MON tests may become the dominant factor under these high efficiency operating conditions. This investigation builds on earlier work to study autoignition behavior over six pressure-temperature (PT) trajectories that correspond to a wide range of operating conditions, including boosted SI operation, partial fuel stratification (PFS), and spark-assisted compression ignition (SACI). A total of 12 different fuels were investigated, including the Co-Optima core fuels and five fuels that represent refinery-relevant blending streams. It was found that, for the ACI operating modes investigated here, the low temperature reactions dominate reactivity, similar to boosted SI operating conditions because their PT trajectories lay close to the RON trajectory. Additionally, the OI metric was found to adequately predict autoignition resistance over the PT domain, for the ACI conditions investigated here, and for fuels from different chemical families. This finding is in contrast with the prior study using a different type of ACI operation with different thermodynamic conditions, specifically a significantly higher temperature at the start of compression, illustrating that fuel response depends highly on the ACI strategy being used.


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