Dynamic Exchange of Substituents in a Prebiotic Organocatalyst: Initial Steps towards an Evolutionary System

Abstract

All evolutionary biological processes lead to a change in heritable traits over successive generations. The responsible genetic information encoded in DNA is altered, selected, and inherited by mutation of the base sequence. While this is well known at the biological level, an evolutionary change at the molecular level of small organic molecules is unknown but represents an important prerequisite for the emergence of life. Here, we present a class of prebiotic imidazolidine-4-thione organocatalysts able to dynamically change their constitution and potentially capable to form an evolutionary system. These catalysts functionalize their building blocks and dynamically adapt to their (selfmodified) environment by mutation of their own structure. Depending on the surrounding conditions, they show pronounced and opposing selectivity in their formation. Remarkably, the preferentially formed species can be associated with different catalytic properties, which enable multiple pathways for the transition from abiotic matter to functional biomolecules.

Organocatalyzed asymmetric dearomative 1,3‐dipolar cycloaddition of 2‐nitrobenzofurans and N‐2,2,2‐trifluoroethylisatin ketimines

“…During the preparation of this manuscript, Albrecht and coworkers also reported the similar reaction with a cinchona‐derived squaramide as the catalyst (18 cases, >20:1 dr and 77–92% ee) 62 . However, after our extensive and in‐depth research, we successfully discovered that a more readily available chiral cyclohexanediamine‐derived bifunctional tertiary amine‐squaramide catalyst 64–66 could readily catalyze the asymmetric dearomative 1,3‐dipolar cycloaddition reaction of 2‐nitrobenzofurans and N ‐2,2,2‐trifluoroethylisatin ketimines in very high efficiency as well as with excellent diastereoselectivity and enantioselectivity (25 examples, up to 99% yield, >20:1 dr in all cases, and 95–99% ee) under mild reaction conditions (Scheme 1). Moreover, this protocol also shows striking features including wide functional group tolerance, great potential for scale‐up synthesis, and attractive product diversification.…”

“…61 During the F I G U R E 1 Selected compounds containing hydrobenzofuran and spirocyclic pyrrolidineoxindole moieties, respectively, and the modular merging strategy for the spiro-fused polyheterocyclic molecular skeletons S C H E M E 1 Readily available chiral cyclohexanediamine-derived bifunctional tertiary aminesquaramide enabling the highly diastereoselective and enantioselective dearomative 1,3-dipolar cycloaddition of 2-nitrobenzofurans and N-2,2,2-trifluoroethylisatin ketimines preparation of this manuscript, Albrecht and coworkers also reported the similar reaction with a cinchonaderived squaramide as the catalyst (18 cases, >20:1 dr and 77-92% ee). 62 However, after our extensive and indepth research, we successfully discovered that a more readily available chiral cyclohexanediamine-derived bifunctional tertiary amine-squaramide catalyst [64][65][66] could readily catalyze the asymmetric dearomative 1,3-dipolar cycloaddition reaction of 2-nitrobenzofurans and N-2,2,2-trifluoroethylisatin ketimines in very high efficiency as well as with excellent diastereoselectivity and enantioselectivity (25 examples, up to 99% yield, >20:1 dr in all cases, and 95-99% ee) under mild reaction conditions (Scheme 1). Moreover, this protocol also shows striking features including wide functional group tolerance, great potential for scale-up synthesis, and attractive product diversification.…”

Formation, stabilization and fate of acetaldehyde and higher aldehydes in an autonomously changing prebiotic system emerging from acetylene

“…The presence of sulfonic acids was also detected in the Murchison meteorite, even though a direct relevance for the origin-of-life remained uncommented 42 . Recent reports show the increased importance of sulfur functional groups, especially thiols, as precursors of protopeptides 43 and organocatalysts 44 .…”

Chemical Cyclic Amplification: Hydroxylamine Boosts the Fenton Reaction for Versatile and Scalable Biosensing

“…6 In the field of biosensing research, nucleic acid detection is undoubtedly one of the most cutting-edge research directions. 7 With the rapid development of molecular biotechnology, nucleic acid detection not only plays an important role in the diagnosis of genetic diseases, 8,9 cancer marker identification, 10 and virus gene detection 11 but also plays an important role in encoding biological genetic information 12 and has also been used in DNA nanotechnology as a programmable building block for building multidimensional self-assembled DNA nanostructures. 13 Achieving ultrahigh sensitivity is the ultimate goal of biological detection in modern analytical science.…”