Competing kinetic pathways in the bromine addition to allylic ethers in 1,2‐dichloroethane: Opposite temperature effects

The kinetics of the electrophilic bromination of three allylic ethers in a nonprotic solvent, 1,2‐dichloroethane, has been investigated. Two of them followed a prevalent second‐order pathway, while the third one exhibited a classical, clean third order. The second‐order pathway in the first two olefins is attributed to electrophilic assistance of the ethereal oxygen to the attacking bromine molecule. In the molecular bromination of 2,4‐cis‐dimethyl‐8‐oxabicyclo[3.2.1]‐6‐octen‐3‐cis‐ol, opposite temperature dependences were found for the two different kinetic pathways. An exoergonic process for the second‐order reaction was explained by the lesser stability of the bromiranium–bromide ionic intermediate, compared to the bromiranium–tribromide in the third‐order profile. © 2007 Wiley Periodicals, Inc. 39: 197–203, 2007     

From chiral and prochiral N-allylpyrroles to stereodefined pyrrole fused architectures: A particular application of the rhodium-catalyzed hydroformylation

We review our recent results on the rhodium-catalyzed hydroformylation of chiral and prochiral N-allylpyrroles as a synthetic route to stereodefined 5,6-dihydro- and 5,6,7,8-tetrahydroindolizines. The indolizine nucleus at different degrees of unsaturation is a building block of natural and synthetic target compounds; thus new approaches, especially if stereoselective and/or stereospecific, are highly desirable. The construction of the indolizine architectures reported here occurs by formation of a C8-C9 bond through intramolecular cyclization of the 4-pyrrolylbutanal intermediate.     

Development and Molecular Understanding of a Pd-Catalyzed Cyanation of Aryl Boronic Acids Enabled by High-Throughput Experimentation and Data Analysis

A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts.     

Modeling and Analysis of Seawater Intrusion in the Coastal Aquifer of Eastern Cap-Bon, Tunisia

A numerical model that treats density-dependent variably saturated flow and miscible salt transport is used to investigate the occurrence of seawater intrusion in the Korba aquifer of the eastern coast of Cap-Bon in northern Tunisia. We examine the interplay between pumping regimes and recharge scenarios and its effect on the saline water distribution. More localized simulations are used to examine, in vertical cross sections, the effects of well location and soil type and the role of the vadose zone in possible remediation actions. The exploratory simulations suggest interesting interactions between the unsaturated zone and the saltwater–freshwater interface with possible implications for groundwater exploitation from shallow unconfined coastal aquifers, involving in one case feedback between seawater intrusion and the high pressure head gradients around the pumping-induced drawdown cone and in another case threshold-like interface displacement for tight soils such as clays. The data processing steps undertaken in this GIS and modeling study are described in some detail, and a critical assessment is given of the data availability and of the requirements for successful monitoring and modeling of seawater intrusion risks in heavily exploited coastal aquifers such as those found in the semi-arid regions of the Mediterranean basin. It is shown how, with the aid of GIS, reasonably reliable information can be assembled from maps, surveys, and other sources of geospatial and hydrogeological data, an approach that is necessary in the many regions of the world with acute water resource problems but with limited means for undertaking systematic data acquisition and environmental monitoring actions. Nonetheless the need for more concerted monitoring of relevant parameters and processes and of closer coordination between monitoring and modeling is stressed. An idea of the extent of over-exploitation of the Korba aquifer is obtained by examining the pumping and rainfall/infiltration data, and the simulation results support groundwater pumping as the mechanism for and seawater intrusion as the origin of the salt contamination observed in the soils and subsurface waters of the Korba plain.     

4-Indolylbutanals from rhodium-catalyzed hydroformylation of allylindoles as precursors of benzofused indolizines

New 4-indolylbutanals have been prepared via a rhodium-catalyzed hydroformylation of differently substituted N-allylindoles. The aldehydes bearing an electron-donating group on the indole nucleus 3-position can evolve into benzofused indolizines via a one pot intramolecular cyclodehydration.     

The VIP Experimental Limit on the Pauli Exclusion Principle Violation by Electrons

In this paper we describe an experimental test of the validity of the Pauli Exclusion Principle (for electrons) which is based on a straightforward idea put forward a few years ago by Ramberg and Snow (Phys. Lett. B 238:438, 1990). We perform a very accurate search of X-rays from the Pauli-forbidden atomic transitions of electrons in the already filled 1S shells of copper atoms. Although the experiment has a very simple structure, it poses deep conceptual and interpretational problems. Here we describe the experimental method and recent experimental results, which we interpret in the framework of quon theory. We also present future plans to upgrade the experimental apparatus using Silicon Drift Detectors.     

VIP-2 —High-Sensitivity Tests on the Pauli Exclusion Principle for Electrons

The VIP collaboration is performing high sensitivity tests of the Pauli Exclusion Principle for electrons in the extremely low cosmic background environment of the underground Gran Sasso National Laboratory INFN (Italy). In particular, the VIP-2 Open Systems experiment was conceived to put strong constraints on those Pauli Exclusion Principle violation models which respect the so-called Messiah–Greenberg superselection rule. The experimental technique consists of introducing a direct current in a copper conductor, and searching for the X-rays emission coming from a forbidden atomic transition from the L shell to the K shell of copper when the K shell is already occupied by two electrons. The analysis of the first three months of collected data (in 2018) is presented. The obtained result represents the best bound on the Pauli Exclusion Principle violation probability which fulfills the Messiah–Greenberg rule.     

A Samarium(II)-mediated, stereoselective cyclization for the synthesis of azaspirocycles

Unsaturated keto-lactams undergo sequential conjugate reduction-aldol cyclization on treatment with SmI 2 to give syn-spirocyclic pyrrolidinones and piperidinones containing vicinal, fully substituted stereocenters with complete diastereocontrol. The substituent on nitrogen and the lactam ring size have a marked impact on the efficiency of the spirocyclization.     

Synthesis of 5,6,7,8‐tetrahydroindolizines via a domino‐type transformation based on the rhodium catalyzed hydroformylation of N‐(β‐methallyl)pyrroles

Variously substituted 5,6,7,8‐tetrahydroindolizines can be easily synthesized via a domino reactions sequence under rhodium catalyzed hydroformylation of N‐(β‐methallyl)pyrroles. The later are readily prepared from properly functionalized pyrroles via phase‐transfer N‐allylation in the presence of 18‐crown‐6 and potassium tert‐butoxide.