Oxazaphospholidine-oxide as an efficient ortho-directing group for the diastereoselective deprotonation of ferrocene

[reaction: see text] Ortho-lithiation of (2R,4S,5R)-3,4-dimethyl-2-ferrocenyl-5-phenyl[1,3,2]oxazaphospholidine 2-oxide 2 was carried out with diastereoselectivity of >99%, affording a new and efficient way for introducing planar chirality into the ferrocene backbone. Various electrophiles were used to quench the lithiated species, showing the wide applicability of the new ortho-directing group and its potential to generate ligands for use in asymmetric catalysis.     

Topological invariants in the study of a chaotic food chain system

The study of ecological systems has generated deep interest in exploring the complexity of chaotic food chains. The role of chaos in ecosystems is not entirely understood. One approach to have a better comprehension of ecological chaos is by analyzing it in mathematical models of basic food chains. In this article it is considered a classical chaotic food chain model from the literature. We use the theory of symbolic dynamics to study the topological entropy and the parameter space ordering of kneading sequences associated with one-dimensional maps that reproduce significant aspects of the model dynamics. The topological entropy allows us to distinguish different chaotic states in some realistic system parameter region. Another numerical invariant is introduced in order to characterize isentropic dynamics. Studying a set of maps with the same topological entropy, we exhibit numerical results about the relation between the second topological invariant and each of the control parameters in consideration. This work provides an illustration of how our understanding of ecological models can be enhanced by the theory of symbolic dynamics.     

A General Acid‐Mediated Hydroaminomethylation of Unactivated Alkenes and Alkynes

In comparison to the extensively studied metal‐catalyzed hydroamination reaction, hydroaminomethylation has received significantly less attention despite its considerable potential to streamline amine synthesis. State‐of‐the‐art protocols for hydroaminomethylation of alkenes rely largely on transition‐metal catalysis, enabling this transformation only under highly designed and controlled conditions. Here we report a broadly applicable, acid‐mediated approach to the hydroaminomethylation of unactivated alkenes and alkynes. This methodology employs cheap, readily available, and bench‐stable reactants and affords the desired amines with excellent functional group tolerance and impeccable regioselectivity. The broad scope of this transformation, as well as mechanistic investigations and in situ domino functionalization reactions are reported.     

Vinyl Cation Stabilization by Silicon Enables a Formal Metal‐Free α‐Arylation of Alkyl Ketones

The ability of silicon to stabilize vinyl cationic species leads to a redox arylation of alkynes whereby the stringent limitations of reactivity and regioselectivity of alkyl‐substituted alkynes are lifted. This allows the synthesis of a range of α‐silyl‐α′‐arylketones under mild conditions in good to excellent yields and with high functional group tolerance, whereby the silicon moiety in the final products can either be removed for a formal acetone monoarylation transform, or capitalized upon for subsequent electrophilic substitutions at either side of the carbonyl group.     

Selective Recognition of Amino Acids and Peptides by Small Supramolecular Receptors

To this day, the recognition and high affinity binding of biomolecules in water by synthetic receptors remains challenging, while the necessity for systems for their sensing, transport and modulation persists. This problematic is prevalent for the recognition of peptides, which not only have key roles in many biochemical pathways, as well as having pharmacological and biotechnological applications, but also frequently serve as models for the study of proteins. Taking inspiration in nature and on the interactions that occur between several receptors and peptide sequences, many researchers have developed and applied a variety of different synthetic receptors, as is the case of macrocyclic compounds, molecular imprinted polymers, organometallic cages, among others, to bind amino acids, small peptides and proteins. In this critical review, we present and discuss selected examples of synthetic receptors for amino acids and peptides, with a greater focus on supramolecular receptors, which show great promise for the selective recognition of these biomolecules in physiological conditions. We decided to focus preferentially on small synthetic receptors (leaving out of this review high molecular weight polymeric systems) for which more detailed and accurate molecular level information regarding the main structural and thermodynamic features of the receptor biomolecule assemblies is available.     

Generative Art with Swarm Landscapes

We present a generative swarm art project that creates 3D animations by running a Particle Swarm Optimization algorithm over synthetic landscapes produced by an objective function. Different kinds of functions are explored, including mathematical expressions, Perlin noise-based terrain, and several image-based procedures. A method for displaying the particle swarm exploring the search space in aesthetically pleasing ways is described. Several experiments are detailed and analyzed and a number of interesting visual artifacts are highlighted.