Recent advances in the catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides

Catalytic asymmetric 1,3-dipolar cycloadditions of azomethine ylides have turned out to be one of the most efficient methods for the preparation of enantioenriched pyrrolidines. The past decade has witnessed the development of a bunch of well-defined catalytic systems capable of affording excellent diastereo and enantioselectivities. Recently, a great effort has been focused on expanding the scope of the cycloaddition with regard to both reaction partners. In this review, we will discuss important advances that have been reported in this area since 2011The Ministerio de Economía y Competitividad (MINECO, project CTQ2012-3579) and Consejería de Educación de la Comunidad de Madrid (programme AVANCAT; S2009/PPQ-1634

Catalytic asymmetric synthesis of diazabicyclo[3.1.0]hexanes by 1,3-dipolar cycloaddition of azomethine ylides with azirines

Substituted 1,3-diazabicyclo[3.1.0]hexanes with two contiguous quaternary stereocentres are readily prepared by catalytic asymmetric [3+2] cycloaddition of α-substituted iminoesters with azirines. High diastereoselectivities and enantioselectivities (up to 98% ee) are achieved using CuI/(R)-Fesulphos as the catalytic systemWe thank the Spanish Ministerio de Economía, Industria y Competitividad (Grant CTQ2015-66954-P, MINECO/FEDER, UE) and FEDER/Ministerio de Ciencia, Innovación y Universidades – Agencia Estatal de Investigación (Grant PGC2018-098660-B-I00) for financial suppor

Anti-hydroarylation of activated internal alkynes: merging pd and energy transfer catalysis

A general catalytic anti-hydroarylation of electron-deficient internal alkynes compatible with both electron-poor and electron-rich aryl reagents is reported. This selectivity is achieved through a sequential syn-carbopalladation of the alkyne by an Ar-Pd species, followed by a tandem, Ir-photocatalyzed, counter-thermodynamic E → Z isomerization. The use of ortho-substituted boronic acids enables direct access to pharmaceutically relevant heterocyclic cores via a cascade process. Mechanistic insight into the involvement of Ar-Pd versus Pd-H as an active species is providedWe thank the Ministerio de Economía, Industria y Competitividad (CTQ2015-66954-P, MINECO/FEDER, UE and FEDER/Ministerio de Ciencia, Innovación y Universidades- ́ Agencia Estatal de Investigación/Proyecto PGC2018-098660- ́ B-I00) for financial suppor

Transition-metal-catalyzed functionalization of alkynes with organoboron reagents: new trends, nechanistic insights, and applications

Catalytic functionalization of alkynes with organoboron reagents provides a straightforward access to stereochemically defined multisubstituted alkenes, which are structural motifs commonly found in bioactive compounds and organic materials. Recent progress has substantially broadened the scope of this field on several fronts. Strategies for regioselectivity control in the 1,2-migratory insertion across unsymmetrical internal alkynes, as well as for the direct access to products with anti-insertion stereochemistry, have been devised. The alkenyl-to-aryl 1,4-metal migration upon metal insertion has been recently exploited in powerful cascade sequences leading to complex polycyclic scaffolds, including the development of enantioselective processes. Elegant enantiospecific and dynamic kinetic resolution methods have been developed for accessing chiral allenes from propargylic alcohol derivatives. Mechanistic manifolds have emerged based on single-electron transfer (SET) that have provided a fresh impetus for alkyne 1,2-difunctionalization with complementary stereoselectivity to processes relying on 1,2-insertion of R-M species. Herein, we discuss the most recent advances in transition-metal-catalyzed functionalization of alkynes using organoboron reagents, categorized according to the type of mechanistic outcome. Emphasis is placed on mechanistic aspects, synthetic utility, limitations, and challenges for future researchWe thank the Ministerio de Ciencia e Innovación (MICINN) and Fondo Europeo de Desarrollo Regional (FEDER, UE) for financial support (Agencia Estatal de Investigación/Project PGC2018-098660-B-I00). J.C. thanks the Ministerio de Educación, Cultura y Deporte (MECD), for an FPU fellowship. Inés Manjón is gratefully acknowledged for her assistance with the final edition of the manuscrip

Synthesis of alkylidene pyrrolo[3,4-b]pyridin-7-one derivatives via RhIII-catalyzed cascade oxidative alkenylation/annulation of picolinamides

A practical RhIII-catalyzed cascade olefination/annulation of picolinamides leading to pyrrolo[3,4-b]pyridines has been developed. The reaction shows wide scope, complete regiocontrol and excellent stereoselectivityWe thank Spanish Government (MINECO, CTQ2012-35790) and Madrid regional government (AVANCAT, S2009/PPQ-1634) for financial support. N.R. thanks the MICINN for a Ramón y Cajal contract and the Marie Curie Foundation (CIG: CHAAS- 304085

Copper-catalyzed ortho-C-H amination of protected anilines with secondary amines

A practical Cu-catalyzed picolinamide-directed o-amination of anilines showing excellent mono-substitution selectivity and high functional group tolerance has been developedWe thank the Spanish Government (MINECO, CTQ2012-35790) and the Madrid regional government (AVANCAT, S2009/PPQ-1634) for financial support. N.R. thanks the MICINN for a Ramon y Cajal contract and the Marie Curie Foundation (CIG: CHAAS-304085

Cobalt-Catalyzed ortho-C−H functionalization/alkyne annulation of benzylamine derivatives: Access to dihydroisoquinolines

A practical picolinamide-directed C−H functionalization/alkyne annulation of benzylamine derivatives enabling access to the previously elusive 1,4-dihydroisoquinoline skeleton was developed using molecular O2as the sole oxidant and Co(OAc)2as precatalyst. The method is compatible with both internal and terminal alkynes and shows high versatility and functional-group tolerance. Furthermore, full preservation of enantiopurity is observed when using non-racemic α-substituted benzylamine derivatives. Kinetic analysis of the reagents and catalyst, labeling experiments, and the isolation and identification of catalytically competent Co-complexes revealed important insights about the mechanismWe thank the Spanish Ministerio de Economía, Industriay Competitividad (MINECO,Grants CTQ2012-35790andCTQ2015-66954-P,MINECO/FEDER,UE) for financial support.N.R. thanks the MICINN for a Ramón y Cajal contract and the European Commission for a Marie Curie Career Integration Grant (CIG:CHAAS-304085

Flora vascular de la Sierra de Mendaur.

Se ha estudiado la flora vascular de un área representativa de la Navarra silícea: la Sierra del Mendaur. El catálogo elaborado comprende 561 táxones de los cuales, más de una veintena se citan por primera vez para Navarra

Palladium-Catalyzed Remote ortho-C-H Alkenylation of Alkyl Aryl Sulfones: Access to Densely Functionalized Indane Derivatives

This is the peer-reviewed version of the following article: Advanced Synthesis and Catalysis 358.7 (2016): 1065-1072, which has been published in final form at http://dx.doi.org/10.1002/adsc.201501129. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-ArchivingA practical method for the palladium-cat-alyzed ortho-olefination of benzyl and phenethyl 2-pyridyl sulfones with electron-deficient alkenes using N-fluoro-2,4,6-trimethylpyridinium triflate ([F+]) as the terminal oxidant is described. The che-lating auxiliary (2-pyridyl)sulfonyl unit was demon-strated to be the key to the success of this reaction, which occurs efficiently with excellent regioselectiv-ity and monosubstitution selectivity. A variety of steric and electronic changes to both coupling part-ners is tolerated, including substitution at the ben-zylic position of the sulfone compound. Further-more, no appreciable loss of enantiopurity is ob-served when using non-racemic substrates. This method provides access to indane derivatives hold-ing three contiguous stereogenic centers with high diastereocontrol. The indane framework was con-structed by intramolecular Michael addition of the a-sulfonyl carbanion to the electrophilic alkeneWe thank the Spanish Government (MINECO, CTQ2012- 35790) for financial support. P.D. L. thanks the Spanish Government (MINECO) for an FPU predoctoral fellowshi

Overview of Neutrino–Nucleus Interactions

Neutrino–nucleus reactions are surveyed. The approximations usually made are identified and a comparison to the corresponding electron–nucleus processes is presented. Impulse Approximation (IA), factorization of the cross-section and scaling approaches (SA) to lepton–nucleus scattering are examined in detail