Organocatalytic synthesis of axially chiral atropisomers

This review summarises the recent progress made in the organocatalytic synthesis of atropisomeric compounds. Methodologies based on dynamic kinetic resolution and direct access to BINOL-like biaryls are described. A particular emphasis is given to reaction mechanisms and to the development of strategies to obtain stable products by increasing the barrier to atropisomer interconversion during the reaction

Synthesis, characterization and antifungal assessment of optically active bis-organotin compounds derived from (S)-BINOL diesters

Background: Organotin(IV) derivatives have appeared recently as potential biologically active metallopharmaceuticals exhibiting a variety of therapeutic activities. Hence, it is important to study the synthesis of new organotin compounds with low toxicity that may be of pharmacological interest.Objectives:This study focuses on the synthesis of new bis-stannylated derivatives with C2 symmetry that could be tested as antifungal agents against two clinical important fungal species, Cryptococcus neoformans and Candida albicans.Methods:The radical addition of triorganotin hydrides (R3SnH) and diorganotin chlorohydrides (R2ClSnH) to bis-α,β-unsaturated diesters derived from (S)-BINOL led to the corresponding new bis-stannylated derivatives with C2 symmetry. Nine pure organotin compounds were synthesized with defined stereochemistry. Four of them were enantiomerically pure and four were diastereoisomeric mixtures.Results:All new organotin compounds were fully characterized, those with phenyl ligands bonded to tin were the most active compounds against both the strains (Cryptococcus neoformans and Candida albicans), with activity parameters of IC50 close to those of the reference drug (amphotericin B).Conclusion:Nine pure organotin compounds with C2 symmetry were synthesized with defined stereochemistry and their antifungal properties were tested against two clinical important fungi with IC values close to those of the reference drug. The structure-containing preferably two or three phenyl groups joined to the tin atom were highly active against both the strains compared with those possessing tri-n-butyl groups.Fil: Costantino, Andrea Rosana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Neudörfl, Jörg M.. Universitat zu Köln; Alemania. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; ArgentinaFil: Ocampo, Romina Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Svetaz, Laura Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; ArgentinaFil: Zacchino, Susana Alicia Stella. Universitat zu Köln; AlemaniaFil: Koll, Liliana Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Mandolesi, Sandra Delia. Universidad Nacional del Sur; Argentin

N-Triflylphosphorimidoyl Trichloride: A Versatile Reagent for the Synthesis of Strong Chiral Brønsted Acids

A series of strong Brønsted acids has been synthesized in high yields using N-triflylphosphorimidoyl trichloride as reagent. The syntheses proceed efficiently with electron-rich, electron-deficient, and sterically hindered substrates

Synthesis of Solution-Phase Phosphoramidite and Phosphite Ligand Libraries and Their In Situ Screening in the Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids

Herein, we report the automated parallel synthesis of solution-phase libraries of phosphoramidite ligands for the development of enantioselective catalysts. The ligand libraries are screened in situ in the asymmetric rhodium-catalyzed addition of arylboronic acids to aldehydes and imines. It is shown that the described methodology results in the straightforward discovery of leads for highly efficient enantioselective catalysts.

Pemberdayaan Aparatur Pemerintah Daerah di Dinas Pekerjaan Umum Kabupaten Bolaang Mongondow Utara

Kantor Dinas Pariwisata Kabupaten Bolaang Mongondow Utara sebagai salahsatu satuan kerja perangkat pemerintah daerah mempunyai tugas dalammemberdayakan aparatur pemerintah daerah, oleh sebab itu dalam hal pemberdayaan,aparatur dituntut untuk lebih profesional dan maksimal agar tujuan-tujuan dari instansidapat tercapai dengan baik dan dapat memberikan pelayanan yang maksimal kepadamasyarakat.Penelitian ini secara umum bertujuan untuk mengetahui pemberdayaanaparatur pemerintah daerah pada Dinas Pariwisata serta faktor-faktor apa saja yangmempengaruhi, dapat dilihat dari faktor pendukung dan faktor penghambat. Metodepenelitian yang digunakan dalam penelitian ini adalah metode penelitian kualitatiftanpa menggunakan hipotesa.Berdasarkan hasil penelitian yang dilakukan dan dilanjutkan denganmenganalisa data, maka dapat disimpulkan bahwa Pemberdayaan AparaturPemerintah Daerah pada Dinas Pariwisata Kabupaten Bolaang Mongondow Utarasudah berjalan dengan baik sesuai dengan fokus penelitian yang telah ditentukan

Hydrazones as Singular Reagents in Asymmetric Organocatalysis

This Minireview summarizes strategies and developments regarding the use of hydrazones as reagents in asymmetric organocatalysis, their distinct roles in nucleophile–electrophile, cycloaddition, and cyclization reactions. The key structural elements governing the reactivity of these reagents in a preferred pathway will be discussed, as well as their different interactions with organocatalysts, leading to diverse activation modes. Along these studies, the synthetic equivalence of N-monoalkyl, N,N-dialkyl, and N-acyl hydrazones with several synthons is also highlighted. Emphasis is also put on the mechanistic studies performed to understand the observed reactivities. Finally, the functional group transformations performed from the available products has also been analyzed, highlighting the synthetic value of these methodologies, which served to access numerous families of valuable multifunctional compounds and nitrogen-containing heterocycles.Ministerio de Economía y Competitividad CTQ2013-48164-C2-1-P, CTQ201348164-C2-2-PEuropean FEDER fundsJunta de Andalucía 2012/FQM 107

Phosphoramidite Gold(I)-Catalyzed Diastereo- and Enantioselective Synthesis of 3,4-Substituted Pyrrolidines

In this article the utility of phosphoramidite ligands in enantioselective AuI catalysis was explored in the development of highly diastereo- and enantioselective AuI-catalyzed cycloadditions of allenenes. A Au^I-catalyzed synthesis of 3,4-disubstituted pyrrolidines and γ-lactams is described. This reaction proceeds through the enantioselective AuI-catalyzed cyclization of allenenes to form a carbocationic intermediate that is trapped by an exogenous nucleophile, resulting in the highly diastereoselective construction of three contiguous stereogenic centers. A computational study (DFT) was also performed to gain some insight into the underlying mechanisms of these cycloadditions. The utility of this new methodology was demonstrated through the formal synthesis of (−)-isocynometrine

Chiral separation by enantioselective liquid–liquid extraction

The literature on enantioselective liquid–liquid extraction (ELLE) spans more than half a century of research. Nonetheless, a comprehensive overview has not appeared during the past few decades. Enantioselective liquid–liquid extraction is a technology of interest for a wide range of chemists and chemical engineers in the fields of fine chemicals, pharmaceuticals, agrochemicals, fragrances and foods. In this review the principles and advances of resolution through enantioselective liquid–liquid extraction are discussed, starting with an introduction on the principles of enantioselective liquid–liquid extraction including host–guest chemistry, extraction and phase transfer mechanisms, and multistage liquid–liquid extraction processing. Then the literature on enantioselective liquid–liquid extraction systems is reviewed, structured on extractant classes. The following extractant classes are considered: crown ether based extractants, metal complexes and metalloids, extractants based on tartrates, and a final section with all other types of chiral extractants.

Proposal : Organokatalysatoren für die fluorige biphasische Katalyse ; Möglichkeiten der homogenen Katalyse mit anschließendem Katalysator‐Recycling

Übertragung des Konzeptes der fluorigen biphasischen Systeme bzw. Übergangsmetallkatalyse auf die fluorige biphasische Organokatalyse. Entwicklung neuer Organokatalysatoren für dieses neuartige Katalysekonzept auf der Basis bereits bekannter Taddol, Thioharnstoff und Binolphosphat-Katalysatoren. Synthese der vorgestellten fluorigen Organokatalysatoren. Einsatzgebiete, Katalysatorrecycling.A new Concept in Organocatalysis is presented. Fluorous biphasic Organocatalysis, derived from fluorous biphasic systems, is based on commonly used organocatalysts, such as taddol, thiourea, binol-phosphate.synthesis and design of catalysts as well as potential applications and recycling methods are presented