Asymmetric 1,3-Dipolar Cycloadditons of Stabilized Azomethine Ylides with Nitroalkenes

This review highlights the biological importance of many polysubstituted nitro-prolines and -pyrrolidines. Their preparation using asymmetric 1,3-dipolar cycloadditions of azomethine ylides with nitroalkenes using diastereoselective and enantioselective strategies is described remarking the scope and main features of each one.This work has been supported by the Spanish Ministerio de Economía y Competitividad (MINECO) (Consolider INGENIO 2010 CSD2007-00006, CTQ2010-20387), FEDER, Generalitat Valenciana (PROMETEO/2009/039), and by the University of Alicante

Coinage Metal Complexes as Chiral Catalysts for 1,3-Dipolar Cycloadditions

In this account, we describe the experience of our research group in the implementation of chiral coinage metal complexes into the efficient enantioselective 1,3-DC of azomethine ylides derived from α-amino acids and azlactones with different dipolarophiles. The corresponding chiral metallodipoles were generated in situ and next focused on the synthesis of highly substituted prolines. For this purpose, privileged ligands such as phosphoramidites and binap with silver(I), gold(I) and copper(II) salts are described. Depending from the ligand and mainly from the metal salt it can be possible to control the facial endo/exo-diasteroselectivity and the enantioselectivity of these types of processes. The synthetic processes are also supported by DFT calculations in order to elucidate the most plausible mechanism and the stereochemical results.This work has been supported by the Spanish Ministerio de Economía y Competitividad (MINECO) (Consolider INGENIO 2010 CSD2007-00006, CTQ2010-20387), FEDER, Generalitat Valenciana (PROMETEO/2009/039), and by the University of Alicante

1,3-Dipolar cycloadditions of azomethine imines

Azomethine imines are considered 1,3-dipoles of the aza-allyl type which are transient intermediates and should be generated in situ but can also be stable and isolable compounds. They react with electron-rich and electron-poor olefins as well as with acetylenic compounds and allenoates mainly by a [3 + 2] cycloaddition but they can also take part in [3 + 3], [4 + 3], [3 + 2 + 2] and [5 + 3] with different dipolarophiles. These 1,3-dipolar cycloadditions (1,3-DC) can be performed not only under thermal or microwave conditions but also using metallo- and organocatalytic systems. In recent years enantiocatalyzed 1,3-dipolar cycloadditions have been extensively considered and applied to the synthesis of a great variety of dinitrogenated heterocycles with biological activity. Acyclic azomethine imines derived from mono and disubstituted hydrazones could be generated by prototropy under heating or by using Lewis or Brønsted acids to give, after [3 + 2] cycloadditions, pyrazolidines and pyrazolines. Cyclic azomethine imines, incorporating a C–N bond in a ring, such as isoquinolinium imides are the most widely used dipoles in normal and inverse-electron demand 1,3-DC allowing the synthesis of tetrahydro-, dihydro- and unsaturated pyrazolo[1,5-a]isoquinolines in racemic and enantioenriched forms with interesting biological activity. Pyridinium and quinolinium imides give the corresponding pyrazolopyridines and indazolo[3,2-a]isoquinolines, respectively. In the case of cyclic azomethine imines with an N–N bond incorporated into a ring, N-alkylidene-3-oxo-pyrazolidinium ylides are the most popular stable and isolated dipoles able to form dinitrogen-fused saturated and unsaturated pyrazolopyrazolones as racemic or enantiomerically enriched compounds present in many pharmaceuticals, agrochemicals and other useful chemicals.We acknowledge continued financial support from the Ministerio de Ciencia e Innovación (MICINN) (projects CTQ2007-62771/BQU, CTQ2010-20387, CONSOLIDER INGENIO 2010-CDS2007-00006, CTQ2011-24151, and CTQ2011-24165), the Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P, CTQ2014-51912-REDC, and CTQ2014-53695-P), FEDER, the Generalitat Valenciana (PROMETEO 2009/039 and PROMETEOII/2014/017), and the University of Alicante

Evaluation of crowdsourcing Wi-Fi radio map creation in a real scenario for AAL applications

Indoor location at room level plays a key role for providing useful services for Ambient Assisted Living (AAL) applications. Wi-Fi fingerprinting indoor location methods are extensively used due to the widespread availability of WiFi infrastructures. A main drawback of Wi-Fi fingerprinting methods is the temporal cost involved in creating the radio maps. Crowdsourcing strategies have been presented as a way to minimize the cost of radio map creation. In this work, we present an extensive study of the issues involved when using crowdsourcing strategies for that purpose. Results provided by extensive experiments performed in a real scenario by three users during two weeks are presented. The main conclusions are: i) crowdsourcing data improves accuracy location in most studied cases; ii) accuracy of Wi-Fi fingerprinting methods decay along time; iii) device diversity is an important issue even when using the same device model

Impact of the Moral Recovery Program for Drug Surrenderees in Cavite

The main objective of the study is to evaluate the impact of the moral-recovery program done by different religious organizations in cooperation with the Dangerous Drugs Board (DDB) of the Philippines, Philippine National Police, Local Governments Units, and Non-Government Agencies and various business sectors.  A total of 131 drug surenderees from Cavite, Philippines were purposively selected to participate in the study. One hundred fourteen (87%) respondents are male and 17 (13%) are female. Survey questionnaires and interviews were used to gather the data to find out how the program made an impact to the morality of the surrenderees. Frequency and percentages were used for statistical analysis. Results showed that after attending the 3-month moral recovery program, 111 (85%) of the drug surenderees resolved to stop using drugs, 64 (49%) committed to attend church regularly, 98 (75%) have a better relationship with God, and 23 (18%) have a healthier perspective in life and became more responsible members of their own families. The respondents, who were influenced by their friends to use drugs, after attending the 12-session moral recovery program that lasted for three months, changed their lives dramatically from turning to drugs to turning to God in solving their problems. This proved that the program helped the drug surenderees to improve their lives and relationship with God and with other people. Since this program is mandated by the government, it is recommended that further studies on the impact of the moral recovery program in other areas in the Philippines be done

Enhanced catalytic activity of natural hematite-supported ppm levels of Pd in nitroarenes reduction

In this work, Pd NPs supported on amine-modified natural hematite have been prepared and characterized. Using this simple catalyst, nitroaromatic compounds as a major cause of industrial pollution were reduced to corresponding amines with ppm levels of Pd in the presence of designer surfactant TPGS-750-M and NaBH4 at room temperature in aqueous media. Synergistic effect between hematite and Pd is responsible for the observed enhanced catalytic activity. This catalyst was recycled for at least four times with a small decrease in the activity.The authors are grateful to Institute for Advanced Studies in Basic Sciences (IASBS) Research Council and Iran National Science Foundation (INSF-Grant number of 97021804) for support of this work. We also gratefully acknowledge financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEOII/2014/017) and the University of Alicante

Heterocycle-based bifunctional organocatalysts in asymmetric synthesis

Different chiral bifunctional organocatalysts derived from trans-cyclohexane-1,2-diamine bearing different types of guanidine units able to form-hydrogen bonding activation have been designed. Conformational rigid 2-aminobenzimidazoles bearing a tertiary amino group have been used in enantioselective Michael type reactions of activated methylene compounds to nitroalkenes. The C2 symmetric bis(2-aminobenzimidazole) derivatives the appropriate organocatalyst for the conjugate addition of 1,3-dicarbonyl compounds to maleimides as well as for the SN1 reaction of benzylic alcohols with carbon nucleophiles. 2-Aminobenzimidazoles bearing a primary amino group have shown excellent catalytic activity in the Michael reaction of aldehydes to maleimides and nitroalkenes. Diastereomeric 2-aminopyrimidines bearing a prolinamide unit have been incorporated in the trans-cyclohexane-1,2-diamine scaffold and have been used for the inter- and intra-molecular direct aldol reaction under solvent-free conditions. For the Michael reaction of aldehydes with maleimides the primary amine 2-aminopyrimidine has shown excellent efficiency as organocatalyst. The bifunctional character of these organocatalysts has been demonstrated by means of DFT calculations.The Spanish Ministerio de Ciencia e Innovación (MICINN) (projects CTQ2010-20387, and Consolider Ingenio 2010, CSD2007-00006), the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), FEDER, the Generalitat Valenciana (PROMETEO 2009/039 and PROMETEOII/2014/017), the Basque Government (GV Grant IT-291-07), the FP7 Marie Curie Actions of the European Commission via the ITN ECHONET network (MCITN-2012-316379) and the Universities of Alicante and Basque Country are gratefully acknowledged for financial support. We also thank for technical and human support provided by IZO-SGI SGIker of UPV-EHU and European funding (ERDF and ESF)

First Reusable Catalyst for the Reductive Coupling Reaction of Organohalides with Aldehydes

In this study, we simulate the reductive coupling (Barbier–Grignard-type) reaction of organohalides with aldehydes using a new reusable catalyst. In this regard, bimetallic alloys of NiCo encapsulated in melamine-based dendrimers (MBD) immobilized on magnetic nanoparticles symbolized as γ-Fe2O3-MBD/NiCo were designed and synthesized. The structure and properties of the catalyst were studied by a variety of techniques such as Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), energy-dispersive spectrometry (EDS) mapping, and inductively coupled plasma (ICP). The presence of NiCo nanoalloys was confirmed by XRD and XPS analysis, TEM images, and EDS mapping. Various secondary alcohols were produced in good to high yields by reductive coupling of different types of aldehydes and organohalides in the presence of HCO2K as a nonmetallic reducing agent in aqueous media catalyzed by γ-Fe2O3-MBD/NiCo. In these reactions, the high catalytic performance of γ-Fe2O3-MBD/NiCo was achieved in comparison to monometallic counterparts due to the synergistic cooperative effect of Co and Ni in the NiCo nanoalloys. Magnetic and hydrophilic properties of the catalyst facilitate the catalyst recyclability for seven runs. The reusability of γ-Fe2O3-MBD/NiCo, use of water as an environmentally friendly solvent, ease of processing, and absence of metal additives make this process an excellent choice for the reductive coupling reaction to produce secondary alcohols from aldehydes. This is the first report on these kinds of reactions using a reusable catalyst.Financial support for this project was acknowledged by the Birjand University Research Council

High Performance Magnetically Separable G‐C3N4/γ‐Fe2O3/TiO2 Nanocomposite with Boosted Photocatalytic Capability towards the Cefixime Trihydrate Degradation under Visible‐Light

A magnetically separable g‐C3N4/γ‐Fe2O3/TiO2 nanocomposite is synthesized as an intensely effectual visible‐light‐driven photocatalyst. It is fully characterized by FT‐IR, XPS, XRD, VSM, DRS, SEM, TEM, BET, EDS, and elemental mapping techniques. Based on the Tauc plot of (αhν)2 vs. hυ, the value of band gap energy for g‐C3N4/γ‐Fe2O3/TiO2 is estimated to be 2.6 eV, which proves the high capability of the catalyst to enhance the photoinduced electron‐holes separation and improves its visible‐light photocatalytic performance. The high photocatalytic activity of this catalyst towards the cefixime trihydrate (CEF) degradation, under visible‐light radiation can be ascribed to the synergistic optical effects between g‐C3N4, γ‐Fe2O3, and TiO2. Using central composite design (CCD) based on response surface methodology (RSM), the maximum degradation efficiency of about 98 % was obtained at the optimal conditions comprising the CEF amount of 20 mg/L, photocatalyst value of 0.04 g/L, irradiation intensity of 9 W/m2, and pH of 5.5, at 90 min. Utilizing an innocuous visible‐light source, almost complete mineralization of CEF (based on TOC analysis), using a very low amount of photocatalyst, applying air as the oxidant, and convenient magnetic separation of the catalyst from the reaction media and its ease of recycling for at least seven consecutive runs are the major highlights of this protocol.Financial support of this project by the University of Birjand Research Council and the XPS facilities of the University of Alicante is appreciated

Binap-silver-catalyzed enantioselective multicomponent 1,3-dipolar cycloaddition of azomethines ylides derived from ethyl glyoxylate

The enantioselective binap–silver catalyzed multicomponent 1,3-dipolar cycloaddition using ethyl glyoxylate, phenylalanine ethyl ester, and maleimides is described. The employment of basic silver carbonate allows the reaction to take place in the absence of an extra base giving high yields and ee. In addition, low-level calculations regarding the importance of the benzyl substituent at the α-position of the amino ester justify the expected absolute configuration of the final cycloadducts and the observed high enantiodiscrimination.Financial support was provided by the Spanish Ministerio de Ciencia e Innovación (MICINN) (projects CTQ2010-20387, and Consolider Ingenio 2010, CSD2007-00006), the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P, and CTQ2014-51912-REDC), FEDER, the Generalitat Valenciana (PROMETEO 2009/039 and PROMETEOII/2014/017), and the University of Alicante