Carboxylic Acid Deoxyfluorination and One-Pot Amide Bond Formation Using Pentafluoropyridine (PFP)

This work describes the application of pentafluoropyridine (PFP), a cheap commercially available reagent, in the deoxyfluorination of carboxylic acids to acyl fluorides. The acyl fluorides can be formed from a range of acids under mild conditions. We also demonstrate that PFP can be utilized in a one-pot amide bond formation via in situ generation of acyl fluorides. This one-pot deoxyfluorination amide bond-forming reaction gives ready access to amides in yields of ≤94%

Quasiparticle tunneling spectroscopy of high {Tc} cuprates

Superconductor-insulator-normal metal (SIN) and superconductor-insulator-superconductor (SIS) tunnel junctions provide important information on pairing state symmetry and mechanism. Measurements of such junctions on high {Tc} superconductors (HTS) are reported using mechanical point contacts, which generally display the optimum characteristics that can be obtained from HTS native-surface tunnel barriers. New tunneling data on the infinite-layer cuprate, Sr{sub 1{minus}x}Nd{sub x}CuO{sub 2} are reported which show a remarkable similarity to another electron-doped cuprate, Nd{sub 1.85}Ce{sub 0.85}CuO{sub 4}. In particular, there is a strong, asymmetric linear background conductance that is indicative of inelastic tunneling from a continuum of states. A discussion is given of the anomalous dip feature found in the tunneling and photoemission data on BSCCO 2212. It is shown that a similar feature is found in many cuprate junctions and that this dip scales with the gap energy over a wide range. New data on the single-layer, tetragonal cuprate, Tl{sub 2}Ba{sub 2}CuO{sub 6} (Tl2201) are presented and discussed in light of recent published results on the similar compound HgBa{sub 2}CuO{sub 4} (Hg1201). The HG1201 data display a low, flat sub-gap tunneling conductance which is consistent with a BCS density of states whereas the T12201 data display a cusp-like feature at zero bias which is more consistent with d{sub x}2-{sub y}2 symmetry

Multimessenger astronomy with the Einstein Telescope

Gravitational waves (GWs) are expected to play a crucial role in the development of multimessenger astrophysics. The combination of GW observations with other astrophysical triggers, such as from gamma-ray and X-ray satellites, optical/radio telescopes, and neutrino detectors allows us to decipher science that would otherwise be inaccessible. In this paper, we provide a broad review from the multimessenger perspective of the science reach offered by the third generation interferometric GW detectors and by the Einstein Telescope (ET) in particular. We focus on cosmic transients, and base our estimates on the results obtained by ET's predecessors GEO, LIGO, and Virgo.Comment: 26 pages. 3 figures. Special issue of GRG on the Einstein Telescope. Minor corrections include

Tetrafluoropyridyl (TFP): a general phenol protecting group readily cleaved under mild conditions

Phenols are extremely valuable building blocks in the areas of pharmaceuticals, natural products, materials and catalysts. In order to carry out modifications on phenols, the phenolic oxygen is routinely protected to prevent unwanted side reactions. Presently many of the protecting groups available can require harsh conditions, specialist equipment, expensive or air/moisture-sensitive reagents to install and remove. Here we introduce the use of the tetrafluoropyridyl (TFP) group as a general protecting group for phenols. TFP can be installed in one step with no sensitivity to water or air, and it is stable under a range of commonly employed reaction conditions including acid and base. The TFP protecting group is readily cleaved under mild conditions with quantitative conversion to the parent phenol, observed in many cases in less than 1 hour

Synthesis of Complex Unnatural Fluorine-Containing Amino Acids

The area of fluorinated amino acid synthesis has seen rapid growth over the past decade. As reports of singly fluorinated natural amino acid derivatives have grown, researchers have turned their attention to develop methodology to access complex proteinogenic examples. A variety of reaction conditions have been employed in this area, exploiting new advances in the wider synthetic community such as photocatalysis and palladium cross-coupling. In addition, novel fluorinated functional groups have also been incorporated into amino acids, with SFX and perfluoro moieties now appearing with more frequency in the literature. This review focuses on synthetic methodology for accessing complex non-proteinogenic amino acids, along with amino acids containing multiple fluorine atoms such as CF3, SF5 and perfluoroaromatic groups

One-pot ester and thioester formation mediated by pentafluoropyridine (PFP)

Acyl fluorides are valuable synthetic intermediates, but in some cases they can be challenging to handle and difficult to isolate given their susceptibility to degradation. In addition, many reagents utilised to prepare acyl fluorides are incompatible with in situ generation strategies and require the acyl fluoride to be isolated before any further reaction can take place. The combination of these factors has meant that acyl fluorides are currently under investigated in nucleophilic substitution processes, and often only a limited substrate scope is tolerated where they have been used. Herein, we report that pentafluoropyridine can be utilised to generate acyl fluorides in situ under mild conditions, and that they can subsequently be used to generate a range of esters and thioesters. This methodology offers a simple one-pot synthesis of esters and thioesters directly from parent carboxylic acids