198 research outputs found
Elektrokatalytische formale C(sp 2 )−H Alkylierung via Nickel‐katalysierter elektrophiler Kreuzkupplung mit vielseitigen Arylsulfoniumsalzen
No full textAbstract Die Synthese sp 3 ‐hybridsierter kohlenstoffreicher Moleküle ist aufgrund ihrer Bedeutung und ihres Erfolgs insbesondere in klinischen Studien von besonderem Interesse. In dieser Arbeit wurde das Einbringen von aliphatischen Ketten auf ein aromatisches Gerüst durch eine Nickel‐katalysierte C(sp 2 )−C(sp 3 ) elektrophile Kreuzkupplungen mit Arylsulfoniumsalzen erreicht. So konnten einfach, nichtpräfunktionalisiere Arene durch die Bildung von Aryldibenzothiopheniumsalze alkyliert werden. Durch den elektrochemischen Ansatz können potenziell gefährliche chemische Redoxreagenzien vermieden werden. Insbesondere die Ein‐Topf Alkylierung erwies sich als praktikabel, was die Robustheit unseres Ansatzes unterstreicht.H2020 European Research Council https://doi.org/10.13039/100010663Deutsche Forschungsgemeinschaft https://doi.org/10.13039/501100001659H2020 Marie Skłodowska-Curie Actions https://doi.org/10.13039/10001066
Electrocatalytic Formal C(sp2)–H Alkylations via Nickel‐Catalyzed Cross‐Electrophile Coupling with Versatile Arylsulfonium Salts
No full textProducing sp3‐hybridized carbon‐enriched molecules is of particular interest due to their high success rate in clinical trials. The installation of aliphatic chains onto aromatic scaffolds was accomplished by nickel‐catalyzed C(sp2)–C(sp3) cross‐electrophile coupling with arylsulfonium salts. Thus, simple non‐prefunctionalized arenes could be alkylated through the formation of aryldibenzothiophenium salts. The reaction employs an electrochemical approach to avoid potentially hazardous chemical redox agents, and importantly, the one‐pot alkylation proved also viable, highlighting the robustness of our approach
“The media will always have axes to grind but the police have the capacity to project their side of the story better” – Neeraj Kumar
No full textNeeraj Kumar recently retired as the Commissioner of Police Delhi, having served in the Indian Police Service for over 37 years in a wide range of roles. He has now penned his first book, a collection of stories pertaining to high-profile cases solved during his nine year tenure at the Central Bureau of Investigation. Ahead of the London launch of the book, he spoke to Sonali Campion about the IPS, security and corruption in India. Dial D for Don: Inside stories of CBI missions will be launched at the Nehru Centre on 13 July at 6.30pm. The event is free and open to all and will include a panel with leading journalist Owen Bennett Jones and the author. Details here
Weak-coordination-auxiliary aminocatalysis enables directed [3 + 2] cyclization for 2-acylindolizines
No full textA weak-coordination-auxiliary amino-catalyzed approach enables directed [3 + 2] cyclization of α,β-unsaturated ketones and N-heteroaryl ketones for the desired 2-acylindolizines
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an iminium ion/enamine tandem sequence.The synthesis of 2-acylindolizines, possessing a readily modifiable ketone group, is of significant importance as it provides versatile precursors for the preparation of various indolizines. However, due to the electronically less active and more sterically demanding nature of α,β-unsaturated ketones toward iminium formation with an aminocatalyst, the efficient one-pot transformation of α,β-unsaturated ketones for distinct 2-acylindolizines bearing sensitive groups represents a challenge for synthetic chemists. Herein, we report a weak-coordination-auxiliary amino-catalyzed approach that enables directed [3 + 2] cyclization of α,β-unsaturated ketones and N-heteroaryl ketones for the desired 2-acylindolizines
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an iminium ion/enamine tandem sequence. A highly broad range of commercially available α,β-unsaturated ketones (internal, terminal, and cyclic enones) can act as coupling partners for readily accessible 2-acylindolizines relative to the existing state-of-the-art methods. Control experiments and in-depth DFT calculations highlight the importance of weakly coordinated glycine's carboxylic group in promoting the intramolecular cyclization and 1,5-proton transfer processes.A weak-coordination-auxiliary amino-catalyzed approach enables directed [3 + 2] cyclization of α,β-unsaturated ketones and N-heteroaryl ketones for the desired 2-acylindolizines
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an iminium ion/enamine tandem sequence.The synthesis of 2-acylindolizines, possessing a readily modifiable ketone group, is of significant importance as it provides versatile precursors for the preparation of various indolizines. However, due to the electronically less active and more sterically demanding nature of α,β-unsaturated ketones toward iminium formation with an aminocatalyst, the efficient one-pot transformation of α,β-unsaturated ketones for distinct 2-acylindolizines bearing sensitive groups represents a challenge for synthetic chemists. Herein, we report a weak-coordination-auxiliary amino-catalyzed approach that enables directed [3 + 2] cyclization of α,β-unsaturated ketones and N-heteroaryl ketones for the desired 2-acylindolizines
via
an iminium ion/enamine tandem sequence. A highly broad range of commercially available α,β-unsaturated ketones (internal, terminal, and cyclic enones) can act as coupling partners for readily accessible 2-acylindolizines relative to the existing state-of-the-art methods. Control experiments and in-depth DFT calculations highlight the importance of weakly coordinated glycine's carboxylic group in promoting the intramolecular cyclization and 1,5-proton transfer processes.Georg-August-Universität Göttingen https://doi.org/10.13039/501100003385China Scholarship Council https://doi.org/10.13039/501100004543H2020 European Research Council https://doi.org/10.13039/100010663dDeutsche Forschungsgemeinschaft https://doi.org/10.13039/501100001659Deutsches Zentrum für Herz-Kreislaufforschung https://doi.org/10.13039/10001044
Iron‐catalyzed C−H Alkylation/Ring Opening with vinylbenzofurans Enabled by Triazoles
No full textWe report an unprecedented iron‐catalyzed C−H annulation using readily available 2‐vinylbenzofurans as the reaction pattern. The redox‐neutral strategy, based on cheap, non‐toxic and earth abundant iron catalysts, exploits triazole assistance to promote a cascade C−H alkylation, benzofuran ring‐opening and insertion into a Fe−N bond, to form highly functionalized isoquinolones. Detailed mechanistic studies supported by DFT calculations fully disclosed the manifold of the iron catalysis
Fiji:Mental Health Care and Law in an Island Nation
No full textFiji is an island nation in the South Pacific, with a population of less than a million. This chapter examines the impact of the United Nations Convention on the Rights of Persons with Disabilities (CRPD) on mental health law and practice in Fiji, as well as the logistical, economic and cultural barriers to enacting the principles outlined in the CRPD. Several significant advances are described, including reformation and modernisation of the Mental Health Act, 2010, decentralisation of healthcare services, empowerment of community mental health services and a shift towards recovery-centred care. The current mental health landscape includes the nineteenth century St. Giles Hospital in the capital city of Suva, with a Community Mental Health Team (CMHT) and Stress Management Wards in three divisional hospitals. The CMHT, Telemedicine unit and Primary Health Centres collaborate to deliver community-based mental health services. Further decentralisation, specialised clinics for specific populations, Mind Farm and developing St. Giles Hospital into a Regional Institute of Mental Health Care and Research (RIMHCaRe) are other plans taking shape in a phased manner. Unfortunately, resource constraints pose a significant obstacle in fully implementing reforms to align with the CRPD, leaving a gap between legislative aspirations and the practical delivery of mental health services in Fiji. Through an analysis of Fiji’s mental health law and the impact of resource limitations, this chapter sheds light on the complexities and potential solutions for addressing Fijian mental health needs more in line with the principles of the CRPD.</p
Fall Prevention in Postacute Care: Best Practices Versus Documented Practices
No full textAbstract
Date Presented 3/31/2017
Falls are a quality measure under national value-based care initiatives. Thus, this session will present results from a mixed-methods study examining the alignment between best practices and rehabilitation patient documentation to inform future quality initiatives and documentation refinement.
Primary Author and Speaker: Natalie Leland
Contributing Authors: Carin Wong, Jenny Martinez, Brenda Fagan, Kate Wilber, Debra Saliba, Neeraj Sood</jats:p
Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence
No full textAbstract Enantioselective electrocatalysis shows unique potential for the sustainable assembly of enantiomerically enriched molecules. This approach allows electro-oxidative C–H activation to be performed paired to the hydrogen evolution reaction. Recent progress has featured scarce transition metals with limited availability. Here we reveal that the earth-abundant 3 d transition metals nickel and cobalt exhibit distinctive performance for enantioselective electrocatalysis with chemodivergent reactivity patterns. Enantioselective desymmetrizations of strained bicyclic alkenes were achieved through C–H annulations. A data-driven optimization of chiral N , O -bidentate salicyloxazoline-type ligands was crucial for enhancing enantioselectivity in nickel electrocatalysis. Notably, in the transition state of the enantio-determining step, secondary weak attractive π – π and CH– π interactions were identified, reflecting the informed adaptations in the ligand design. Detailed mechanistic investigations by experimental and computational studies revealed for the nickel electrocatalysis a C–N bond-forming reductive elimination from nickel(III) and for the cobalt electrocatalysis a C–C bond-forming nucleophilic addition from cobalt(III) as the product-determining steps
Parametrization of κ 2 - N , O -Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations
No full textDistributed optimization on a wireless sensor network testbed
No full textThe focus of this thesis is to implement various distributed optimization algorithms on a physical wireless sensor network. Distributed optimization refers to optimization of some global function which is not completely known to any single node in a communication network. The global function is some combination of local functions that are available at each node. Therefore the objective is for all nodes to achieve consensus on the global optimum given only local information and communication with neighbors.
Algorithms from the literature that address this problem in different set- tings are introduced, focusing on an incremental subgradient-based algorithm and a broadcast, gossip-based algorithm. These algorithms are applied to lo- calize a light source. This localization problem is formulated as a distributed optimization problem in which the global optimum is the true location of the source, and the local information is comprised of light intensity measurements at each node. Simulation results and results from physical implementations on the testbed are presented for the two different approaches. A modified version of the broadcast algorithm is also presented, and is shown to be supe- rior to the unaltered algorithm in certain settings via simulation and testbed results.Submission published under a 24 month embargo labeled 'U of I only', the embargo will last until 2017-05-01The student, Neeraj Venkatesan, accepted the attached license on 2015-04-23 at 19:16.The student, Neeraj Venkatesan, submitted this Thesis for approval on 2015-04-23 at 19:21.This Thesis was approved for publication on 2015-04-24 at 09:05.DSpace SAF Submission Ingestion Package generated from Vireo submission #8071 on 2015-07-22 at 14:18:45Made available in DSpace on 2015-07-22T22:33:52Z (GMT). No. of bitstreams: 2
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Previous issue date: 2015-04-24Embargo set by: Seth Robbins for item 79905
Lift date: 2017-07-22T22:34:16Z
Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD systemU of I Only Restriction Lifted for Item 79905 on 2017-07-23T09:15:17Z
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