Academic literature on the topic 'Aldehyde and C-H activation'

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Journal articles on the topic "Aldehyde and C-H activation"

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Maia da Silva Santos, Bruno, Mariana dos Santos Dupim, Cauê Paula de Souza, Thiago Messias Cardozo, and Fernanda Gadini Finelli. "DABCO-promoted photocatalytic C–H functionalization of aldehydes." Beilstein Journal of Organic Chemistry 17 (December 21, 2021): 2959–67. http://dx.doi.org/10.3762/bjoc.17.205.

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Herein we present a direct application of DABCO, an inexpensive and broadly accessible organic base, as a hydrogen atom transfer (HAT) abstractor in a photocatalytic strategy for aldehyde C–H activation. The acyl radicals generated in this step were arylated with aryl bromides through a well stablished nickel cross-coupling methodology, leading to a variety of interesting aryl ketones in good yields. We also performed computational calculations to shine light in the HAT step energetics and determined an optimized geometry for the transition state, showing that the hydrogen atom transfer between aldehydes and DABCO is a mildly endergonic, yet sufficiently fast step. The same calculations were performed with quinuclidine, for comparison of both catalysts and the differences are discussed.
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Swamy, V. S. V. S. N., K. Vipin Raj, Kumar Vanka, Sakya S. Sen, and Herbert W. Roesky. "Silylene induced cooperative B–H bond activation and unprecedented aldehyde C–H bond splitting with amidinate ring expansion." Chemical Communications 55, no. 24 (2019): 3536–39. http://dx.doi.org/10.1039/c9cc00296k.

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Xu, Pan, Guoqiang Wang, Zhongkai Wu, Shuhua li, and Chengjian Zhu. "Rh(iii)-catalyzed double C–H activation of aldehyde hydrazones: a route for functionalized 1H-indazole synthesis." Chemical Science 8, no. 2 (2017): 1303–8. http://dx.doi.org/10.1039/c6sc03888c.

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Ochoa, Carmen A., Claire G. Nissen, Deanna D. Mosley, Christopher D. Bauer, Destiny L. Jordan, Kristina L. Bailey, and Todd A. Wyatt. "Aldehyde Trapping by ADX-102 Is Protective against Cigarette Smoke and Alcohol Mediated Lung Cell Injury." Biomolecules 12, no. 3 (March 2, 2022): 393. http://dx.doi.org/10.3390/biom12030393.

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Most individuals diagnosed with alcohol use disorders smoke cigarettes. Large concentrations of malondialdehyde and acetaldehyde are found in lungs co-exposed to cigarette smoke and alcohol. Aldehydes directly injure lungs and form aldehyde protein adducts, impacting epithelial functions. Recently, 2-(3-Amino-6-chloroquinolin-2-yl)propan-2-ol (ADX-102) was developed as an aldehyde-trapping drug. We hypothesized that aldehyde-trapping compounds are protective against lung injury derived from cigarette smoke and alcohol co-exposure. To test this hypothesis, we pretreated mouse ciliated tracheal epithelial cells with 0–100 µM of ADX-102 followed by co-exposure to 5% cigarette smoke extract and 50 mM of ethanol. Pretreatment with ADX-102 dose-dependently protected against smoke and alcohol induced cilia-slowing, decreases in bronchial epithelial cell wound repair, decreases in epithelial monolayer resistance, and the formation of MAA adducts. ADX-102 concentrations up to 100 µM showed no cellular toxicity. As protein kinase C (PKC) activation is a known mechanism for slowing cilia and wound repair, we examined the effects of ADX-102 on smoke and alcohol induced PKC epsilon activity. ADX-102 prevented early (3 h) activation and late (24 h) autodownregulation of PKC epsilon in response to smoke and alcohol. These data suggest that reactive aldehydes generated from cigarette smoke and alcohol metabolism may be potential targets for therapeutic intervention to reduce lung injury.
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Török, Patrik, Dóra Lakk-Bogáth, and József Kaizer. "Stoichiometric Alkane and Aldehyde Hydroxylation Reactions Mediated by In Situ Generated Iron(III)-Iodosylbenzene Adduct." Molecules 28, no. 4 (February 15, 2023): 1855. http://dx.doi.org/10.3390/molecules28041855.

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Previously synthesized and spectroscopically characterized mononuclear nonheme, low-spin iron(III)-iodosylbenzene complex bearing a bidentate pyridyl-benzimidazole ligands has been investigated in alkane and aldehyde oxidation reactions. The in situ generated Fe(III) iodosylbenzene intermediate is a reactive oxidant capable of activating the benzylic C-H bond of alkane. Its electrophilic character was confirmed by using substituted benzaldehydes and a modified ligand framework containing electron-donating (Me) substituents. Furthermore, the results of kinetic isotope experiments (KIE) using deuterated substrate indicate that the C-H activation can be interpreted through a tunneling-like HAT mechanism. Based on the results of the kinetic measurements and the relatively high KIE values, we can conclude that the activation of the C-H bond mediated by iron(III)–iodosylbenzene adducts is the rate-determining step.
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Yuan, Yumeng, Xiemin Guo, Xiaofeng Zhang, Buhong Li, and Qiufeng Huang. "Access to 5H-benzo[a]carbazol-6-ols and benzo[6,7]cyclohepta[1,2-b]indol-6-ols via rhodium-catalyzed C–H activation/carbenoid insertion/aldol-type cyclization." Organic Chemistry Frontiers 7, no. 20 (2020): 3146–59. http://dx.doi.org/10.1039/d0qo00820f.

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Finkelstein, Erik I., Jurjen Ruben, C. Wendy Koot, Milena Hristova, and Albert van der Vliet. "Regulation of constitutive neutrophil apoptosis by the α,β-unsaturated aldehydes acrolein and 4-hydroxynonenal." American Journal of Physiology-Lung Cellular and Molecular Physiology 289, no. 6 (December 2005): L1019—L1028. http://dx.doi.org/10.1152/ajplung.00227.2005.

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Reactive α,β-unsaturated aldehydes are major components of common environmental pollutants and are products of lipid oxidation. Although these aldehydes have been demonstrated to induce apoptotic cell death in various cell types, we recently observed that the α,β-unsaturated aldehyde acrolein (ACR) can inhibit constitutive apoptosis of polymorphonuclear neutrophils and thus potentially contribute to chronic inflammation. The present study was designed to investigate the biochemical mechanisms by which two representative α,β-unsaturated aldehydes, ACR and 4-hydroxynonenal (HNE), regulate neutrophil apoptosis. Whereas low concentrations of either aldehyde (<10 μM) mildly promoted apoptosis in neutrophils (reflected by increased phosphatidylserine exposure, caspase-3 activation, and mitochondrial cytochrome c release), higher concentrations prevented critical features of apoptosis (caspase-3 activation, phosphatidylserine exposure) and caused delayed neutrophil cell death with characteristics of necrosis/oncosis. Inhibition of caspase-3 activation by either aldehyde occurred despite increases in mitochondrial cytochrome c release and occurred in close association with depletion of cellular GSH and with cysteine modifications within caspase-3. However, procaspase-3 processing was also prevented, because of inhibited activation of caspases-9 and -8 under similar conditions, suggesting that ACR (and to a lesser extent HNE) can inhibit both intrinsic (mitochondria dependent) and extrinsic mechanisms of neutrophil apoptosis at initial stages. Collectively, our results indicate that α,β-unsaturated aldehydes can inhibit constitutive neutrophil apoptosis by common mechanisms, involving changes in cellular GSH status resulting in reduced activation of initiator caspases as well as inactivation of caspase-3 by modification of its critical cysteine residue.
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Zhang, Qiao, Angela Bell-Taylor, Fraser M. Bronston, John D. Gorden, and Christian R. Goldsmith. "Aldehyde Deformylation and Catalytic C–H Activation Resulting from a Shared Cobalt(II) Precursor." Inorganic Chemistry 56, no. 2 (December 22, 2016): 773–82. http://dx.doi.org/10.1021/acs.inorgchem.6b02127.

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Seo, Jia, Che-Wei Chen, Shih-Ching Chuang, Jung Min Joo, Woohyeong Lee, Ju Eun Jeon, and Pei-Ling Chen. "Palladium-Catalyzed C–H Benzannulation of Functionalized Furans and Pyrroles with Alkynes." Synthesis 53, no. 17 (May 6, 2021): 3001–10. http://dx.doi.org/10.1055/a-1502-3641.

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AbstractA benzannulation strategy involving activation of two C–H bonds of five-membered heteroarenes was developed. Readily available furans and pyrroles stabilized by synthetically useful electron-withdrawing groups underwent Pd-catalyzed 1:2 annulation reactions with diaryl alkynes. A variety of functional groups, including ester, amide, ketone, aldehyde, and nitrile, on the heterocyclic cores were tolerated in the Pd-catalyzed oxidative reactions. In these reactions, the combination of 2,2-dimethylbutyric acid and its conjugate base facilitated metalation at the heteroaromatic rings and reoxidation of the Pd(0) species using oxygen as the terminal oxidant. This strategy provides fluorescent ­benzofuran and indole derivatives and is expected to allow for further development of functionalized polycyclic heteroaromatic compounds.
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Hill, Jeremy P., Paul D. Buckley, Leonard F. Blackwell, Richard M. Sime, and Richard L. Kingston. "Activation of aldehyde dehydrogenase at physiological temperatures." Biochemical Pharmacology 44, no. 12 (December 1992): 2425–26. http://dx.doi.org/10.1016/0006-2952(92)90692-c.

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Dissertations / Theses on the topic "Aldehyde and C-H activation"

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Henderson, William Howell. "Palladium-Mediated C-H Activations." The Ohio State University, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=osu1318003095.

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Chudasama, V. "The use of aerobic aldehyde C-H activation for the construction of C-C and C-N bonds." Thesis, University College London (University of London), 2011. http://discovery.ucl.ac.uk/1324525/.

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This thesis describes a series of studies directed towards the use of aerobic aldehyde C-H activation for the construction of C-C and C-N bonds by the process of hydroacylation. Chapter 1 provides an introduction to the research project and an overview of strategies for hydroacylation. Chapter 2 describes the application of aerobic aldehyde C-H activation for the hydroacylation of vinyl sulfonates and sulfones. A discussion on the mechanism of the transformation, the effect of using aldehydes with different oxidation profiles and the application of chiral aldehydes is also included. Chapter 3 describes the functionalisation of γ-keto sulfonates with particular emphasis on an elimination/conjugate addition strategy, which provides an indirect approach to the hydroacylation of electron rich alkenes. Chapters 4 and 5 describe the application of aerobic aldehyde C-H activation towards the hydroacylation of α,β-unsaturated esters and vinyl phosphonates, respectively. An in-depth discussion on the mechanism and aldehyde tolerance of each transformation is also included. Chapter 6 describes acyl radical approaches towards C-N bond formation with particular emphasis on the synthesis of amides and acyl hydrazides.
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Akhbar, A. R. "Hydroacylation of N=N bonds via aerobic C-H activation of aldehydes, and reactions of the products thereof." Thesis, University College London (University of London), 2014. http://discovery.ucl.ac.uk/1456292/.

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The development of methods to construct new chemical bonds efficiently and selectively whilst minimising energy usage and waste production is of high importance in organic chemistry. Many current methods employ inefficient, costly and often toxic multi step protocols to generate new chemical bonds. The hydroacylation reaction is one method of reducing such inefficiencies. The development of an aerobic hydroacylation protocol in the Caddick group has recently allowed the functionalisation of aldehydes with a wide array of electron deficient alkenes. This process relies on trapping an acyl radical intermediate, from the auto-oxidation of aldehydes to acids, with a suitable alkene. Since aldehyde auto-oxidation takes place readily in the presence of atmospheric oxygen, the aerobic hydroacylation reaction can be conducted in aqueous media in the absence of any additional reagents. Following on from previous work in the group, this thesis describes studies towards expanding the scope of this novel methodology in the formation of C-N bonds. It also assesses the scalability of this reaction in order to make acyl hydrazides for further chemical transformations; as such, the development of protocols for the conversion of acyl hydrazides to carboxylic acid derivatives and to ketones will also be described. Chapter 1 provides an introduction to and a general overview of current methods of hydroacylation and acid derivative syntheses. Chapter 2 describes the development of conditions for, and application of aerobic hydroacylation towards C N bond formation, and the scalability of the hydroacylation reaction. Chapter 3 will focus on solving the failures of previous attempts for the conversion of acyl hydrazides to tertiary amides. Chapter 4 will demonstrate the applicability of acyl hydrazides to the synthesis of carboxylic esters and describe some of its limitations. Finally, chapter 5 will reveal acyl hydrazides as a new class of precursors for the chemoselective synthesis of ketones.
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Weeks, Amanda. "C-H activation in organic synthesis." Thesis, University of Bristol, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.535205.

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Doyle, Claire Marie. "C-H activation reactions of tetrahydropyridines." Thesis, Imperial College London, 2012. http://hdl.handle.net/10044/1/9469.

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This thesis is presented as five chapters: Chapter 1.0 is divided into two sections: the first is a review of palladium-catalysed C–C bond forming reactions. It covers palladium-catalysed cross-coupling reactions; C–H bond functionalisation; the Heck reaction and functionalisation of heteroaromatic C–H bonds. Secondly the use of tetrahydropyridines in organic synthesis is discussed, with a particular focus on methodology developed by the Craig group. Chapter 2.0 discusses the research carried out during this studentship. It is divided into six sections and discusses the results obtained from research efforts into: our initial strategy for tetrahydropyridine synthesis; an SN1 approach; an α,β-unsaturated lactam approach; synthesis of 3-methoxy aryl-substituted tetrahydropyridines; synthesis of heteroaromatic analogues and further elaboration of tricyclic tetrahydropyridines. Chapter 3.0 details future work proposed within the areas described above. Chapter 4.0 details the experimental procedures employed and spectroscopic data for the compounds discussed in chapter 2.0. Finally, chapter 5.0 lists the references sourced in this thesis.
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Vastine, Benjamin Alan. "Understanding mechanisms for C-H bond activation." [College Station, Tex. : Texas A&M University, 2008. http://hdl.handle.net/1969.1/ETD-TAMU-2679.

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Khamker, Qudsia. "Ambiphilic C-H activation routes to heterocycles." Thesis, University of Leicester, 2014. http://hdl.handle.net/2381/28919.

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This thesis describes investigations of Cp*Rh- and (p-Cy)Ru-catalysed C-H functionalisation reactions of various substrates with alkynes and alkenes for the formation of several heterocycles and carbocycles. Mechanistic studies and DFT calculations are also presented. Chapter One includes a discussion of different mechanisms of C-H activation namely oxidative addition, σ-bond metathesis, 1,2-addition, electrophilic activation and AMLA/CMD. The applications of these different mechanisms of C-H activation in catalysis are also discussed with a particular emphasis on the use of AMLA/CMD in direct arylation reactions. Chapter Two gives an overview of stoichiometric and catalytic studies of AMLA C-H activation and subsequent reactivity with alkynes at Ir, Rh, and Ru. The results of Cp*Rh- and some (p-Cy)Ru-catalysed reactions of C-phenylpyrazoles with alkynes are presented. N-H and C-H activation occurs, leading to heterocycles. Mechanistic studies and DFT calculations show that C-H activation is reversible and rate limiting in the cases examined. Chapter Three is similar to Chapter Two but focusses on reactions with alkenes. The Cp*Rh-catalysed reactions of C-phenylpyrazoles with alkenes lead to mono or divinyl products which may undergo further aza-Michael cyclisations if the alkene is a good Michael acceptor. Mechanistic studies and DFT calculations are also discussed. Chapter Four deals with Cp*Rh-catalysed coupling reactions of other directing groups, including imidazole, imidazoline, pyrazolidinone, hydrazine, carboxylic acid and oxime with alkynes. Again, there is discussion on the different factors affecting product selectivity. Chapter Five gives a summary of all the conclusions on the work presented in this thesis. Throughout the thesis, all new compounds are characterised spectroscopically and several compounds have been characterised by X-ray crystallography.
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Wiley, Jack Scott. "C-H bond activation in iridium complexes /." Thesis, Connect to this title online; UW restricted, 1999. http://hdl.handle.net/1773/8510.

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Bu, Qingqing. "Ruthenium- and Cobalt-Catalyzed C-H Activation." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2018. http://hdl.handle.net/11858/00-1735-0000-002E-E4FC-F.

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Moselage, Marc Philipp. "C-H and C-C Activation by Cobalt and Ruthenium Catalysis." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2017. http://hdl.handle.net/11858/00-1735-0000-0023-3FB2-6.

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Books on the topic "Aldehyde and C-H activation"

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Yu, Jin-Quan, Lutz Ackermann, and Zhangjie Shi. C-H activation. Heidelberg: Springer, 2010.

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Yu, Jin-Quan, and Zhangjie Shi, eds. C-H Activation. Berlin, Heidelberg: Springer Berlin Heidelberg, 2010. http://dx.doi.org/10.1007/978-3-642-12356-6.

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C-H activation. Heidelberg: Springer, 2010.

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R, Leone Stephen, and United States. National Aeronautics and Space Administration., eds. Rate coefficients of C₂H with C₂H₄, C₂H₆, and H₂ from 150 to 359 K. [Washington, DC: National Aeronautics and Space Administration, 1996.

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Goldberg, Karen I., and Alan S. Goldman, eds. Activation and Functionalization of C—H Bonds. Washington, DC: American Chemical Society, 2004. http://dx.doi.org/10.1021/bk-2004-0885.

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Dixneuf, Pierre H., and Henri Doucet, eds. C-H Bond Activation and Catalytic Functionalization II. Cham: Springer International Publishing, 2016. http://dx.doi.org/10.1007/978-3-319-29319-6.

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Dixneuf, Pierre H., and Henri Doucet, eds. C-H Bond Activation and Catalytic Functionalization I. Cham: Springer International Publishing, 2016. http://dx.doi.org/10.1007/978-3-319-24630-7.

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Wu, Xiao-Feng, ed. Transition Metal-Catalyzed Heterocycle Synthesis via CH Activation. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA, 2016. http://dx.doi.org/10.1002/9783527691920.

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Pérez, Pedro J., ed. Alkane C-H Activation by Single-Site Metal Catalysis. Dordrecht: Springer Netherlands, 2012. http://dx.doi.org/10.1007/978-90-481-3698-8.

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Matsumoto, Arimasa. Iron-Catalyzed Synthesis of Fused Aromatic Compounds via C–H Bond Activation. Tokyo: Springer Japan, 2014. http://dx.doi.org/10.1007/978-4-431-54928-4.

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Book chapters on the topic "Aldehyde and C-H activation"

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Li, Jie Jack. "C–H activation." In Name Reactions, 112–22. Cham: Springer International Publishing, 2014. http://dx.doi.org/10.1007/978-3-319-03979-4_54.

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Shi, Feng, and Richard C. Larock. "Remote C–H Activation via Through-Space Palladium and Rhodium Migrations." In C-H Activation, 123–64. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/128_2008_46.

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Daugulis, Olafs. "Palladium and Copper Catalysis in Regioselective, Intermolecular Coupling of C–H and C–Hal Bonds." In C-H Activation, 57–84. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/128_2009_10.

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Davies, Huw M. L., and Allison R. Dick. "Functionalization of Carbon–Hydrogen Bonds Through Transition Metal Carbenoid Insertion." In C-H Activation, 303–45. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/128_2009_11.

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Bouffard, Jean, and Kenichiro Itami. "Rhodium-Catalyzed C–H Bond Arylation of Arenes." In C-H Activation, 231–80. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/128_2009_12.

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Martins, Andrew, Brian Mariampillai, and Mark Lautens. "Synthesis in the Key of Catellani: Norbornene-Mediated ortho C–H Functionalization." In C-H Activation, 1–33. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/128_2009_13.

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Fagnou, Keith. "Mechanistic Considerations in the Development and Use of Azine, Diazine and Azole N-Oxides in Palladium-Catalyzed Direct Arylation." In C-H Activation, 35–56. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/128_2009_14.

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Beck, Elizabeth M., and Matthew J. Gaunt. "Pd-Catalyzed C–H Bond Functionalization on the Indole and Pyrrole Nucleus." In C-H Activation, 85–121. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/128_2009_15.

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Liu, Guosheng, and Yichen Wu. "Palladium-Catalyzed Allylic C–H Bond Functionalization of Olefins." In C-H Activation, 195–209. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/128_2009_16.

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Yoo, Woo-Jin, and Chao-Jun Li. "Cross-Dehydrogenative Coupling Reactions of sp3-Hybridized C–H Bonds." In C-H Activation, 281–302. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/128_2009_17.

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Conference papers on the topic "Aldehyde and C-H activation"

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Ulin-Avila, Erick, and Akhilesh Kumar Mishra. "Graphene-based Photonic C-H bond activation." In Frontiers in Optics. Washington, D.C.: OSA, 2021. http://dx.doi.org/10.1364/fio.2021.jtu1a.55.

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Nyambo, Silver, Dong-Sheng Yang, and Yuchen Zhang. "PROBING SELECTIVE BOND ACTIVATION IN ALKYLAMINES: LANTHANUM-MEDIATED C-H AND N-H BOND ACTIVATION STUDIED BY MATI SPECTROSCOPY." In 73rd International Symposium on Molecular Spectroscopy. Urbana, Illinois: University of Illinois at Urbana-Champaign, 2018. http://dx.doi.org/10.15278/isms.2018.fb01.

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Kim, Jongsik, Marshall S. Abbott, David B. Go, and Jason C. Hicks. "Tunable C-H activation via metal-plasma interaction at elevated temperatures." In 2016 IEEE International Conference on Plasma Science (ICOPS). IEEE, 2016. http://dx.doi.org/10.1109/plasma.2016.7533960.

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Ortiz de Elguea, Verónica, Nuria Sotomayor, and Esther Lete. "Intramolecular Palladium-catalyzed C-H activation reactions: Synthesis of substituted quinolones." In MOL2NET 2016, International Conference on Multidisciplinary Sciences, 2nd edition. Basel, Switzerland: MDPI, 2016. http://dx.doi.org/10.3390/mol2net-02-h008.

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Kim, Jong, and Dong-Sheng Yang. "YTTRIUM-ASSISTED C-H AND C-C BOND ACTIVATION OF ETHYLENE PROBED BY MASS-ANALYZED THRESHOLD IONIZATION SPECTROSCOPY." In 71st International Symposium on Molecular Spectroscopy. Urbana, Illinois: University of Illinois at Urbana-Champaign, 2016. http://dx.doi.org/10.15278/isms.2016.ri06.

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Lian, T., S. E. Bromberg, H. Yang, M. Asplund, R. G. Bergman, and C. B. Harris. "Femtosecond IR Studies of Alkane C-H Bond Activation by Organometallic Compounds." In International Conference on Ultrafast Phenomena. Washington, D.C.: Optica Publishing Group, 1996. http://dx.doi.org/10.1364/up.1996.fe.27a.

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The mechanism of alkane C-H bond activation by transition metal complexes such as CpM(CO)2 (M=Rh, Ir) has been intensely studied because it represents a first step in a catalytic process using unreactive hydrocarbons.[1] The bond activation reaction starts with the formation of monocarbonyl intermediates such as CpRh(CO). These species have been detected in the gas phase[2] and in liquefied rare Kr and Xe[3] by µs time resolved IR spectroscopy. Unfortunately, the subsequent oxidative insertion of CpRh(CO) into the C-H bond is not well understood due to its rapid rate and low quantum yield (~1%) for formation of the C-H activated product. These properties have hindered previous femtosecond and picosecond time-resolved studies of activation reaction in room temperature alkane solution. [4]
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Kim, Jong, and Dong-Sheng Yang. "SPECTROSCOPIC IDENTIFICATION OF Y(C4H6) ISOMERS FORMED BY YTTRIUM-MEDIATED C-H BOND ACTIVATION OF BUTENES." In 71st International Symposium on Molecular Spectroscopy. Urbana, Illinois: University of Illinois at Urbana-Champaign, 2016. http://dx.doi.org/10.15278/isms.2016.mh09.

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Akkerman, JW N. "INTRACELLULAR PH CHANGES AND PLATELET ACTIVATION." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1644774.

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It is long known that platelet aggregation and secretion are accompanied by acidification of the extracellular medium. Much of the proton extrusion results from hydrolysis of ATP generated in the glycolytic pathway and liberation of secretion granules, which are slightly acidic. Recent eyidence points at a third source for extracellular protons.Following early observations (1) that epinephrine-induced platelet functions depended on extracellular Na+ (Na+ o ), it became evident that platelets possess a Na+ /H+ antiport, which regulates the cytosolic pH (pH.) via stochiometric exchange of intracellular protons with extracellular Na+ (2). Platelet functions triggered by epinephrine, AdP or low doses of thrombin are impaired by (i) the absence of Na+ o, and (ii) the presence of EIPA, an amiloride analogue which blocks the antiport. Ionophores which enhance proton efflux enhance the platelet responses. Thus, the antiport affects platelet functions via changes in pHi, but this has been difficult to establish experimentally. Early studies by Simons based on 6-carboxyfluorescein indeed reported a rise in pHi. during platelet activation, but more precise analysis awaited the development of more sensitive pHi-indicators. Recently (3),1studies employing BCECF, have confirmed that resting platelets maintain a pH. of about 7.1 via an EIPA-sensitive mechanism.Platelet activation induces a rise of 0.1-0.2 pH units, which lasts for several minutes unless the antiport is inhibited. When Na+/H+ exchange is gradually inhibited by lowering Na+ o , EIPA-sensitive proton efflux, mobilization of Ca2+ ions and aggregation are inhibited in parallel following stimulation with a low dose of thrombin. Artificial alkalinization reverses these effects. Alkalinization alone is not a trigger for platelet functions. Furthermore, high doses of thrombin (> 0.2 U/ml) initiate Ca2+ -mobilization and aggregation independent of changes in pHi Possibly, Na+ /H+ exchange enhances Ca mobilization by inositol-P3, generated by weak stimulation of the thrombin receptor, wfiich accords with the pH profile of IP3-induced Ca2+ liberation from isolated dense tubular membranes. However, concurrent measurement of Quin-2 and BCECF-fluoresence indicate that Ca2+ mobilization slightly precedes the rise in pHi which would make Ca+ mobilization a trigger for Na+ /H+ exchange is stead of one of its effects. Recent data favour a role for protein kinase C in activation of the antiport. A rise in pHi. is seen during incubation with OAG, an activator of protein kinase C. Thrombin (low dose)-induced Na /H exchange is inhibited by TFP, an inhibitor of this enzyme. These findings are bes^explained by assuming that low doses of thrombin initiate phospholipase C-mediated formation of inositol-P3, which triggers Ca2+ mobilization. Concurrently, diacylglycerol is formed, which activates protein kinase C. The result is a rise in pHi, which enhances the mobilization of Ca2+ by inositol-P3.This scheme differs from the sequence seen during activation by ADP or epinephrine (1), where Na+ /H2+ exchange is an early step after receptor occupancy and precedes phospholipid A2-mediated PG-endoperoxides/TxA2 formation. These metabolites activate phospholipase C resulting in diacylglycerol and inositol-P3-formation at a rather late stage in signal processing. Recent evidence (4) indicates that in epinephrine-stimulated platelets Na+ /H+ exchange requires fibrinogen binding, which opens the intriguing possibility that occupancy of GPIIb-IIIa starts a process that affects signal processing pathways in platelets.Sweatt, J.D., Limbird, L.E, et al. J.B.C. 1983, 1985, 1986Siffert, W., Akkerman, J.W.N., et al. FEBS Lett 1984, 1987; Nature 1987.Zavoico, G.B., Feinstein, M.B st al. J.B.C. 1986Banga, H.D., Rittenhouse, S.E. PNAS 1986
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9

Siffert, W., P. Scheid, and JW N. Akkerman. "PROTEIN KINASE C CONTROLS CA2+ MOBILIZATION IN HUMAN PLATELETS." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1644509.

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Platelet stimulation has been shown to result in a rise of cytosolic pH (pHi) as a result of an activation of a Na+/H+ antiport. We have investigated the role of pH in Ca2+ mobilization in human platelets. pHi and free Ca2+, {Ca2+)i, were measured in platelets loaded with the fluorescent indicators BCECF and quin2, respectively. Stimulation of platelets by either thrombin or OAG, an activator of protein kinase C (Pk-C), increased pHi. Pretreatment of platelets with inhibitors of Pk-C, trifluoperazine (TFP) or sphingosine (SPH), blocked the stimulus-induced rise in pHi, suggesting a role of Pk-C in the activation of Na+/H+ exchange. Blocking Na+/H+ exchange by an amiloride analogue or by TFP similarly suppressed the thrombin-induced increase in {Ca2*}i. This effect could be prevented by increasing pHi with the Na+/H+ ionophore monensin or with NH4Cl. The thrombin-induced (0.05 U/ml) rise in {Ca2+}i was more than 3-fold enhanced when the pH was raised from 6.8 to 7.4.Our results demonstrate that pHi controls Ca2+ mobilization in human platelets and suggest that Pk-C contributes to this control by activating the Na+/H+ exchanger.Supported by the Deutsche Forschungsgemeinschaft. No Sche 46/5-2.
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Marbet, G. A., P. Satiropas, C. Pantaleoni, and F. Duckert. "SECONDARY FIBRINOLYSIS, PROTEIN C ACTIVATION, PLATELET DECREASE, BUT NOT CONTACT ACTIVATION CAN BE CORRELATED TO FREE THROMBIN ACTION IN EXPERIMENTAL DIC." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1643576.

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We have studied the influence of activated coagulation on antithrombotic defence mechanisms in vivo. Conventional coagulation variables, platelets (Tcy), plasminogen (Pig), α2-antiplasmin (AP) , protein C (PC), factor VIII C, factor XII and Cl-inhibitor have been measured before and during reversible tissue thromboplastin-induced DIC in the dog. Free thrombin action as derived from fibrinogen (Fbg) decrease has been expressed as integral of active thrombin concentration over time (φ). Protection by heparin H, pentosan polysulfate PPS or dermatan sulfate DS was studied. DIC had no consistent effect on the behaviour of factor XII and Cl-inhibitor, but led to the consumption (Δ) of the following variables:The Spearman correlation coefficients between and φ in the Δ whole group were all statistically significant and ranged from rs=0.51 (ΔPlg) to rs =0.94 (ΔFbg). The response of major defense mechanisms in vivo quantitatively depends on active thrombin.
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Reports on the topic "Aldehyde and C-H activation"

1

Lees, Alistair J. Photochemistry of Intermolecular C-H Bond Activation Reactions. Office of Scientific and Technical Information (OSTI), June 2000. http://dx.doi.org/10.2172/761218.

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2

Rakowski-DuBois, Mary C. Aspects of C-H Activation in Metal Complexes Containing Sulfur Ligands. Office of Scientific and Technical Information (OSTI), October 2004. http://dx.doi.org/10.2172/833244.

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3

Asplund, M. C. Time resolved infrared studies of C-H bond activation by organometallics. Office of Scientific and Technical Information (OSTI), June 1998. http://dx.doi.org/10.2172/290889.

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4

Crabtree, Robert. Moving to Sustainable Metals: Multifunctional Ligands in Catalytic, Outer Sphere C-H, N-H and O-H Activation. Office of Scientific and Technical Information (OSTI), March 2015. http://dx.doi.org/10.2172/1171638.

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5

Das, Jayabrata, and Debabrata Maiti. Transition Metal Catalyzed Remote C-H Activation: A New Direction Towards Site-Selective Chemical Reactions. The Israel Chemical Society, March 2023. http://dx.doi.org/10.51167/acm00036.

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6

Lees, A. J. [Photochemistry of intermolecular C-H bond activation reactions]. Progress report, [September 15, 1994--March 15, 1995]. Office of Scientific and Technical Information (OSTI), December 1994. http://dx.doi.org/10.2172/35271.

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Prusky, Dov, Noel T. Keen, and Stanley Freeman. Elicitation of Preformed Antifungal Compounds by Non-Pathogenic Fungus Mutants and their Use for the Prevention of Postharvest Decay in Avocado Fruits. United States Department of Agriculture, January 1996. http://dx.doi.org/10.32747/1996.7570573.bard.

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C. gloeosporioides attacks unripe avocado fruits in the orchard. Germinated spores produce appressoria that germinate and breach the cuticle, but the resultant subcuticular hyphae become quiescent and do not develop further until fruit is harvested and ripens. Resistance of unripe avocado to attach by C. gloeosporioides is correlated with the presence of fungitoxic concentrations of the preformed antifungal compound, 1-acetoxy-2-hydroxy-4-oxoheneicosa-12, 15 diene in the pericarp of unripe fruits. The objective of this proposal was to study the signal transduction process by which elicitors induce resistance in avocado. It was found that abiotic elicitors, infection of avocado fruit with C. gloeosporioides or treatment of avocado cell suspension with cell-wall elicitor induced a significant production of reactive oxygen species (ROS). Ripe and unripe fruit tissue differ with regard to the ROS production. The unripe, resistant fruit are physiologically able to react and to produce high levels of ROS and increased activity of H+ATPase that can enhance the phenylpropanoid pathway ad regulate the levels of the antifungal compound-diene, inhibit fungal development, resulting in its quiescence. Interestingly, it was also found that growth regulators like cytokinin could do activation of the mechanism of resistance. Postharvest treatments of cytokinins strongly activated the phenylpropanoid pathway and induce resistance. We have developed non-pathogenic strains of C. gloeosporioides by Random Enzyme Mediated Integration and selected a hygromycin resistance, non-pathogenic strain Cg-142 out of 3500 transformants. This non-pathogenic isolate activates H+ATPase and induces resistance against Colletotrichum attack. As a basis for studying the importance of PL in pathogenicity, we have carried out heterologous expression of pel from C. gloeosporioides in the non-pathogenic C. magna and determine the significant increase in pathogenicity of the non-pathogenic strain. Based on these results we can state that pectate lyase is an important pathogenicity factor of C. gloeosporioides and found that fungal pathogenicity is affected not by pel but by PL secretion. Our results suggest that PH regulates the secretion of pectate lyase, and support its importance as a pathogenicity factor during the attack of avocado fruit by C. gloeosporioides . This implicates that if these findings are of universal importance in fungi, control of disease development could be done by regulation of secretion of pathogenicity factors.
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Moran, Nava, Richard Crain, and Wolf-Dieter Reiter. Regulation by Light of Plant Potassium Uptake through K Channels: Biochemical, Physiological and Biophysical Study. United States Department of Agriculture, September 1995. http://dx.doi.org/10.32747/1995.7571356.bard.

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The swelling of plant motor cells is regulated by various signals with almost unknown mediators. One of the obligatory steps in the signaling cascade is the activation of K+-influx channels -K+ channels activated by hyperpolarization (KH channels). We thus explored the regulation of these channels in our model system, motor cell protoplasts from Samanea saman, using patch-clamp in the "whole cell" configuration. (a) The most novel finding was that the activity of KH channels in situ varied with the time of the day, in positive correlation with cell swelling: in Extensor cells KH channels were active in the earlier part of the day, while in Flexor cells only during the later part of the day; (b) High internal pH promoted the activity of these channels in Extensor cells, opposite to the behavior of the equivalent channels in guard cells, but in conformity with the predicted behavior of the putative KH channel, cloned from S. saman recently; (c) HIgh external K+ concentration increased (KH channel currents in Flexor cells. BL depolarized the Flexor cells, as detected in cell-attached patch-clamp recording, using KD channels (the K+-efflux channels) as "voltage-sensing devices". Subsequent Red-Light (RL) pulse followed by Darkness, hyperpolarized the cell. We attribute these changes to the inhibition of the H+-pump by BL and its reactivation by RL, as they were abolished by an H+-pump inhibitor. BL increased also the activity KD channels, in a voltage-independent manner - in all probability by an independent signaling pathway. Blue-Light (BL), which stimulates shrinking of Flexor cells, evoked the IP3 signaling cascade (detected directly by IP3 binding assay), known to mobilize cytosolic Ca2+. Nevertheless, cytosolic Ca2+ . did not activate the KD channel in excised, inside-out patches. In this study we established a close functional similarity of the KD channels between Flexor and Extensior cells. Thus the differences in their responses must stem from different links to signaling in both cell types.
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Rafaeli, Ada, and Russell Jurenka. Molecular Characterization of PBAN G-protein Coupled Receptors in Moth Pest Species: Design of Antagonists. United States Department of Agriculture, December 2012. http://dx.doi.org/10.32747/2012.7593390.bard.

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The proposed research was directed at determining the activation/binding domains and gene regulation of the PBAN-R’s thereby providing information for the design and screening of potential PBAN-R-blockers and to indicate possible ways of preventing the process from proceeding to its completion. Our specific aims included: (1) The identification of the PBAN-R binding domain by a combination of: (a) in silico modeling studies for identifying specific amino-acid side chains that are likely to be involved in binding PBAN with the receptor and; (b) bioassays to verify the modeling studies using mutant receptors, cell lines and pheromone glands (at tissue and organism levels) against selected, designed compounds to confirm if compounds are agonists or antagonists. (2) The elucidation ofthemolecular regulationmechanisms of PBAN-R by:(a) age-dependence of gene expression; (b) the effect of hormones and; (c) PBAN-R characterization in male hair-pencil complexes. Background to the topic Insects have several closely related G protein-coupled receptors (GPCRs) belonging to the pyrokinin/PBAN family, one with the ligand pheromone biosynthesis activating neuropeptide or pyrokinin-2 and another with diapause hormone or pyrokinin-1 as a ligand. We were unable to identify the diapause hormone receptor from Helicoverpa zea despite considerable effort. A third, related receptor is activated by a product of the capa gene, periviscerokinins. The pyrokinin/PBAN family of GPCRs and their ligands has been identified in various insects, such as Drosophila, several moth species, mosquitoes, Triboliumcastaneum, Apis mellifera, Nasoniavitripennis, and Acyrthosiphon pisum. Physiological functions of pyrokinin peptides include muscle contraction, whereas PBAN regulates pheromone production in moths plus other functions indicating the pleiotropic nature of these ligands. Based on the alignment of annotated genomic sequences, the primary and secondary structures of the pyrokinin/PBAN family of receptors have similarity with the corresponding structures of the capa or periviscerokinin receptors of insects and the neuromedin U receptors found in vertebrates. Major conclusions, solutions, achievements Evolutionary trace analysisof receptor extracellular domains exhibited several class-specific amino acid residues, which could indicate putative domains for activation of these receptors by ligand recognition and binding. Through site-directed point mutations, the 3rd extracellular domain of PBAN-R was shown to be critical for ligand selection. We identified three receptors that belong to the PBAN family of GPCRs and a partial sequence for the periviscerokinin receptor from the European corn borer, Ostrinianubilalis. Functional expression studies confirmed that only the C-variant of the PBAN-R is active. We identified a non-peptide agonist that will activate the PBAN-receptor from H. zea. We determined that there is transcriptional control of the PBAN-R in two moth species during the development of the pupa to adult, and we demonstrated that this transcriptional regulation is independent of juvenile hormone biosynthesis. This transcriptional control also occurs in male hair-pencil gland complexes of both moth species indicating a regulatory role for PBAN in males. Ultimate confirmation for PBAN's function in the male tissue was revealed through knockdown of the PBAN-R using RNAi-mediated gene-silencing. Implications, both scientific and agricultural The identification of a non-peptide agonist can be exploited in the future for the design of additional compounds that will activate the receptor and to elucidate the binding properties of this receptor. The increase in expression levels of the PBAN-R transcript was delineated to occur at a critical period of 5 hours post-eclosion and its regulation can now be studied. The mysterious role of PBAN in the males was elucidated by using a combination of physiological, biochemical and molecular genetics techniques.
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10

Chemistry of oxygenates on transition metal surfaces: Activation of C- H, C-C, and C-O bonds. Office of Scientific and Technical Information (OSTI), January 1991. http://dx.doi.org/10.2172/7202787.

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