Radiolysis of Solid-State Nitrogen Heterocycles Provides Clues to Their Abundance in the Early Solar System

We studied the radiolysis of a wide variety of N-heterocycles, including many of biological importance, and find that the majority are remarkably stable in the solid-state when subjected to large doses of ionizing gamma radiation from a 60Co source. Degradation of N-heterocycles as a function of dose rate and total dose was measured using high performance liquid chromatography with UV detection. Many N-heterocycles show little degradation when γ-irradiated up to a total dose of ~1 MGy, which approximates hundreds of millions of years’ worth of radiation emitted in meteorite parent bodies due to slow radionuclide decay. Extrapolation of these results suggests that these N-heterocyclic compounds would be stable in dry parent bodies over solar system time-scales. We suggest that the abundance of these N-heterocycles as measured presently in carbonaceous meteorites is largely reflective of their abundance at the time aqueous alteration stopped in their parent bodies, and the absence of certain compounds in present-day samples is either due to the formation mechanisms or degradation which occurred during periods of aqueous alteration or thermal metamorphism

Nitrogen Heterocycles Form Peptide Nucleic Acid Precursors in Complex Prebiotic Mixtures

The ability to store information is believed to have been crucial for the origin and evolution of life; however, little is known about the genetic polymers relevant to abiogenesis. Nitrogen heterocycles (N-heterocycles) are plausible components of such polymers as they may have been readily available on early Earth and are the means by which the extant genetic macromolecules RNA and DNA store information. Here, we report the reactivity of numerous N-heterocycles in highly complex mixtures, which were generated using a Miller-Urey spark discharge apparatus with either a reducing or neutral atmosphere, to investigate how N-heterocycles are modified under plausible prebiotic conditions. High throughput mass spectrometry was used to identify N-heterocycle adducts. Additionally, tandem mass spectrometry and nuclear magnetic resonance spectroscopy were used to elucidate reaction pathways for select reactions. Remarkably, we found that the majority of N-heterocycles, including the canonical nucleobases, gain short carbonyl side chains in our complex mixtures via a Strecker-like synthesis or Michael addition. These types of N-heterocycle adducts are subunits of the proposed RNA precursor, peptide nucleic acids (PNAs). The ease with which these carbonylated heterocycles form under both reducing and neutral atmospheres is suggestive that PNAs could be prebiotically feasible on early Earth

Metal-Free Synthesis of \u3ci\u3eN-Heterocycles via Intramolecular Electrochemical C-H Aminations

N-heterocycles are key structural units in many drugs, biologically interesting molecules and functional materials. To avoid the residues of metal catalysts, the construction of N-heterocycles under metal-free conditions has attracted much research attention in academia and industry. Among them, the intramolecular electrochemical C-H aminations arguably constitute environmentally friendly methodologies for the metal-free construction of N-heterocycles, mainly due to the direct use of clean electricity as the redox agents. With the recent renaissance of organic electrosynthesis, the intramolecular electrochemical C-H aminations have undergone much progress in recent years. In this article, we would like to summarize the advances in this research field since 2019. The emphasis is placed on the reaction design and mechanistic insight. The challenges and future developments in the intramolecular electrochemical C-H aminations are also discussed

Cycloamination strategies for renewable N-heterocycles

Efficient amination strategies for synthesis of N-heterocycles from functional molecules (bottom-up) or from biomass (top-down) via sustainable C–N/C–X bond chemistry

Vibronic fine structure in the nitrogen 1s photoelectron spectra from Franck-Condon simulations. III. Rules for amine/imine N atoms in small N-heterocycles

Vibronic coupling plays a crucial role in X-ray photoelectron spectra (XPS) of molecules. In a series of three papers, we present a comprehensive exploration of the N-heterocycles family, known for their diverse structures, to summarize the general rules of vibronic coupling in high-resolution vibrationally-resolved XPS spectra at the N1s edge. Building upon our previous studies on six-membered monocyclic azines [Phys. Rev. A 106, 022811 (2022)] and fused bicyclic compounds indoles with five and six members [Phys. Rev. A 108, 022816 (2023)], in this study, we focus on investigating a series of 12 five-membered N-heterocycles using Franck-Condon simulations, incorporating Duschinsky rotation effects and density functional theory. Our calculations reveal distinct spectral characteristics of amine and imine within these 12 systems in binding energies, spectral characteristics, structural changes, vibrational coupling strengths, and effects of hydrogenation. Furthermore, we expand our analysis to encompass all 35 N-heterocycles discussed in the three papers and consolidate these findings into the general rules. we find that 1s ionization in amine nitrogen induces more substantial geometrical changes, resulting in larger vibronic coupling strength compared to imine nitrogens. The spectra of imine nitrogens exhibit two distinct characteristic peaks originating from the 0-0 and 0-1 transitions, whereas the spectra of amine nitrogens are characterized by a broad peak with numerous weak fingerprints due to significant mixing of various 0-$n$ transitions. We observe that amine (imine) nitrogens generally cause a negative (positive) change in zero-point vibrational energy. This study provides valuable insights into vibronic coupling in N-heterocycles, shedding light on the distinguishing features and behavior of amine and imine nitrogens in vibrationally-resolved XPS spectra.Comment: 9 figure

Sustainable synthesis of azobenzenes, quinolines and quinoxalines via oxidative dehydrogenative couplings catalysed by reusable transition metal oxide–Bi( iii ) cooperative catalysts

Heterogeneous catalytic oxidative dehydrogenative processes for N-heterocycles are presented, which enable waste-minimized (additive-, oxidant-, base-free), efficient cyclisations/couplings via transition metal oxide–Bi( iii ) cooperative catalysis

Dual role of graphene as support of ligand-stabilized palladium nanoparticles and carbocatalyst for (de)hydrogenation of N-heterocycles

The hybrid material composed of palladium nanoparticles (PdNPs) functionalized with N-heterocyclic carbene ligands (NHCs) immobilized onto the surface of reduced graphene oxide (rGO) results in an efficient catalytic material towards hydrogenation and dehydrogenation of N-heterocycles. The rGO plays a dual role by acting as a carbocatalyst in acceptorless dehydrogenation of N-heterocycles and as a support for the palladium nanoparticles facilitating its interaction with molecular hydrogen turning this hybrid material into an effective hydrogenation catalyst. Hot filtration experiments support the heterogeneous nature of the process underlining the strong interaction of palladium nanoparticles with the graphene enabled by π-interactions of the ligand with the support. The mild conditions used in both transformations of this system without requiring any additives facilitates its potential application in hydrogen storage technologies in the form of liquid organic hydrogen carriers (LOHCs). At the same time, the hybrid material is a robust and efficient catalytic platform that can be recovered and reused up to eight runs in both transformations without significant deactivation. The use of a single solid catalysts that is recyclable in hydrogen conversion and reconversion through (de)hydrogenation of N-heterocycles paves the way for the development of efficient hydrogen storage materials

Zinc – catalyzed reduction of N – heterocycles

Novel bidentate amine – imine, and amido – imine ligands were synthesized. The former species was reacted with ZnMe2 to generate zinc methyl complex. The compound was fully characterized by 1H NMR and X – ray spectroscopy. The zinc methyl complex demonstrated rather limited catalytic activity in hydroboration and hydrosilylation of N – heterocycles. Consequently, a new zinc hydride complex was synthesized using an amido – imine ligand as a precursor. A series of nitrogen heteroaromatics were successfully hydroborated using catalytic amounts of zinc hydride species. Deuterium – labeling experiments, and kinetic studies allowed to get insights into the reaction mechanism. It was proposed that the hydride transfer proceeds via a six – membered transition state orchestrated by the Lewis acidic zinc – hydride complex. Another project was focused on the synthesis of a potentially redox “non – innocent” diimine ligand, using Arduengo’s diketone as the starting point. Attempts to install an imine moiety resulted in a surprising reaction outcome