Prebiotic phosphorylation of (pre)biological substrates under aqueous conditions is a critical step in the origins of life. Previous investigations have had limited success and/or require unique environments which are incompatible with the subsequent generation of the corresponding oligomers or higher order structures. Here we demonstrate that diamidophosphate (DAP), a plausible prebiotic agent produced from trimetaphosphate, efficiently (amido)phosphorylates a wide variety of (pre)biological building blocks (nucleosides/tides, amino acids, and lipid precursors) under aqueous (solution/paste) conditions, without the need of a condensing agent. Significantly, higher order structures (oligonucleotides, peptides and liposomes) are formed under the same phosphorylation reaction conditions. This plausible prebiotic phosphorylation process under similar reaction conditions could enable the systems chemistry of the three classes of (pre)biologically relevant molecules, and their oligomers, in a single-pot aqueous environment.

Phosphorylation under plausible prebiotic conditions continues to be one of the defining issues for the role of phosphorus in the origins of life processes. In this review, we cover the reactions of alternative forms of phosphate, specifically the nitrogenous versions of phosphate (and other forms of reduced phosphorus species) from a prebiotic, synthetic organic and biochemistry perspective. The ease with which such amidophosphates or phosphoramidate derivatives phosphorylate a wide variety of substrates suggests that alternative forms of phosphate could have played a role in overcoming the “phosphorylation in water problem”. We submit that serious consideration should be given to the search for primordial sources of nitrogenous versions of phosphate and other versions of phosphorus.

Model protocells have long been constructed with fatty acids, because these lipids are prebiotically plausible and can, at least theoretically, support a protocell life cycle. However, fatty acid protocells are stable only within a narrow range of pH and metal ion concentration. This instability is particularly problematic as the early Earth would have had a range of conditions, and extant life is completely reliant on metal ions for catalysis and the folding and activity of biological polymers. Here, prebiotically plausible monoacyl cyclophospholipids are shown to form robust vesicles that survive a broad range of pH and high concentrations of Mg2+, Ca2+, and Na+. Importantly, stability to Mg2+ and Ca2+ is improved by the presence of environmental concentrations of Na+. These results suggest that cyclophospholipids, or lipids with similar characteristics, may have played a central role during the emergence of Darwinian evolution.

A simple and inexpensive methodology is reported for the conversion of alkenes to 1,2-dibromo alkanes via oxidative bromination using HBr paired with dimethyl sulfoxide, which serves as the oxidant as well as cosolvent. The substrate scope includes 21 olefins brominated in good to excellent yields. Three of six styrene derivatives yielded bromohydrins under the reaction conditions.

Dimethyl sulfoxide is generally characterized as a solvent and oxidant rather than as a substrate, building block, or synthon in organic chemistry. However, an abundance of reports have recently appeared that demonstrate dimethyl sulfoxide acting in these roles. This review article offers a comprehensive summary of the literature on this topic until the end of 2015. Synthetic transformations that have utilized the 'C-S-C', 'C', and 'C-S' fragments of dimethyl sulfoxide as building blocks are systematically summarized. 1 Introduction 2 History and Recent Highlights of DMSO-Based Oxidations 3 DMSO-Based Methylthiomethylation (-CH 2 SMe) 4 DMSO as a One-Carbon Synthon 4.