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Silver-mediated oxidative functionalization of alkylsilanes.

ABSTRACT: A general approach to the functionalization of aliphatic C-Si bonds in the presence of silver salts and oxidants has been reported. This strategy encompasses a range of valuable C-Si transformations, including the direct conversions of a C-Si bond to C-OCF₃, C-OBz, C-OCOCF₃, C-SCF₃, C-SCN, and C-N₃ bonds. Among them, trifluoromethoxylation of alkylsilanes is reported for the first time. In addition, mechanistic studies indicate that this reaction may proceed through a radical mechanism.

SUBMITTER: Wang F

PROVIDER: S-EPMC6296296 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature

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Silver-mediated oxidative functionalization of alkylsilanes.

Wang Feng F Xu Peng P Cong Fei F Tang Pingping P

Chemical science 20180924 47

A general approach to the functionalization of aliphatic C-Si bonds in the presence of silver salts and oxidants has been reported. This strategy encompasses a range of valuable C-Si transformations, including the direct conversions of a C-Si bond to C-OCF3, C-OBz, C-OCOCF3, C-SCF3, C-SCN, and C-N3 bonds. Among them, trifluoromethoxylation of alkylsilanes is reported for the first time. In addition, mechanistic studies indicate that this reaction may p ...[more]

PMID: 30627401

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Project description:While the use of visible light to drive chemical reactivity is of high importance to the development of environmentally benign chemical transformations, the concomitant use of a stoichiometric electron donor or acceptor is often required to steer the desired redox behavior of these systems. The low-cost and ubiquity of tertiary amine bases has led to their widespread use as reductive additives in photoredox catalysis. Early use of trialkylamines in this context was focused on their role as reductive excited state quenchers of the photocatalyst, which in turn provides a more highly reducing catalytic intermediate. In this Account, we discuss some of the observations and thought processes that have led from our use of amines as reductive additives to their use as complex substrates and intermediates for natural product synthesis. Early attempts by our group to construct key carbon-carbon bonds via free-radical intermediates led to the observation that some trialkylamines readily behave as efficient hydrogen atom donors under redox-active photochemical conditions. In the wake of in-depth mechanistic studies published in the 1970s, 1980s and 1990s, this understanding has in turn allowed for a systematic approach to the design of a number of photochemical methodologies through rational tuning of the amine component. Minimization of the C-H donicity of the amine additive was found to promote desired C-C bond formation in a number of contexts, and subsequent elucidation of the amine's redox fate has sparked a reevaluation of the amine's role from that of reagent to that of substrate. The reactivity of tertiary amines in these photochemical systems is complex, and allows for a number of mechanistic possibilities that are not necessarily mutually exclusive. A variety of combinations of single-electron oxidation, C-H abstraction, deprotonation, and β-scission result in the formation of reactive intermediates such as α-amino radicals and iminium ions. These processes have been explored in depth in the photochemical literature and have resulted in a firm mechanistic grasp of the behavior of amine radical cations in fundamental systems. Harnessing the synthetic potential of these transient species represents an ongoing challenge for the controlled functionalization of amine substrates, because these mechanistic possibilities may result in undesired byproduct formation or substrate decomposition. The presence of tertiary amines in numerous alkaloids, pharmaceuticals, and agrochemicals lends credence to the potential utility of this chemistry in natural product synthesis, and herein we will discuss how these transformations might be controlled for synthetic purposes.

Project description:Fungal metabolites, proteins, and enzymes have been rich sources of therapeutics so far. Therefore, in this study, the hypha extract of a newly identified noble fungus (Alternaria sp. with NCBI Accession number: MT982648) was used to synthesize silver nanoparticles (F-AgNPs) to utilize against bacteria, fungi, and lung cancer. F-AgNPs were characterized by using physical techniques, including UV-visible spectroscopy, zeta potential, DLS, XRD, TEM, and HR-TEM. The particles were found to be polydispersed and quasi-spherical in shape under TEM. They had an average size of ~15 nm. The well dispersed particles were found to have consistent crystallinity with cubic phase geometry under XRD and HR-TEM. The presence of different functional groups on the surfaces of biosynthesized F-AgNPs was confirmed by FTIR. The particle distribution index was found to be 0.447 with a hydrodynamic diameter of ~47 d.nm, and the high value of zeta potential (-20.3 mV) revealed the stability of the nanoemulsion. These particles were found to be active against Staphylococcus aureus (multidrug resistance-MDR), Klebsiella pneumonia, Salmonella abony, and Escherichia coli (MDR) with MIC50 10.3, 12.5, 22.69, and 16.25 µg/mL, respectively. Particles also showed inhibition against fungal strains, including A. flavus, A. niger, T. viridens, and F. oxysporium. Their inhibition of biofilm formation by the same panel of bacteria was also found to be very promising and ranged from 16.66 to 64.81%. F-AgNPs also showed anticancer potential (IC50-21.6 µg/mL) with respect to methotrexate (IC50-17.7 µg/mL) against lung cancer cell line A549, and they did not result in any significant inhibition of the normal cell line BEAS-2. The particles were found to alter the mitochondrial membrane potential, thereby disturbing ATP synthesis and leading to high ROS formation, which are responsible for cell membrane damage and release of LDH, intracellular proteins, lipids, and DNA. A high level of ROS also elicits pro-inflammatory signaling cascades that lead to programmed cell death by either apoptosis or necrosis.

Dataset Information

Silver-mediated oxidative functionalization of alkylsilanes.

Publications

Silver-mediated oxidative functionalization of alkylsilanes.

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