An Aza-Piancatelli Templated Reaction Manifold of 4-Aminocyclopentenones Enables Access to Complex Carbocyclic Assemblies

Capitalizing on the propensity of 1, 2-amino group migration in γ-aminocyclopentenone with a suitable promoter, gem-diaryl equipped systems unfolded an unprecedented avenue for the Lewis acid promoted displacement of γ-aniline group with nucleophiles such as indole. Such transformation, besides providing a means for direct γ-functionalization of cyclopentenones, presented innumerable scope for β, γ-annulation. Various tailored indolo bis-nucleophiles were explored in the current study that rendered an array of indole alkaloid-like compounds in excellent yields and selectivity through one-pot operation. Analysis of collective experimental observation along with designed control experiments strongly suggested the possibility of a retro aza-Piancatelli rearrangement, which is hitherto unknown in the context. Such repertoire could find potential applications in the synthesis of complex assemblies from the Piancatelli rearrangement and related processes. 1. Introduction 2. Aza-Piancatelli rearrangement and related domino processes 3. An unprecedented aza-Piancatelli-templated strategy for polycyclic assemblies 4. Summary and Outlook

Radical trifunctionalization of hexenenitrile by remote cyano migration

A novel radical-mediated trifunctionalization of hexenenitriles by the strategy of remote functional group migration is disclosed. A portfolio of functionalized hexenenitriles are employed as substrates. After difunctionalization of the unactivated...

Spatial modulation of individual behaviors enables an ordered structure of diverse phenotypes during bacterial group migration

Coordination of diverse individuals often requires sophisticated communications and high-order computational abilities. Microbial populations can exhibit diverse individualistic behaviors, and yet can engage in collective migratory patterns with a spatially sorted arrangement of phenotypes. However, it is unclear how such spatially sorted patterns emerge from diverse individuals without complex computational abilities. Here, by investigating the single-cell trajectories during group migration, we discovered that, despite the constant migrating speed of a group, the drift velocities of individual bacteria decrease from the back to the front. With a Langevin-type modeling framework, we showed that this decreasing profile of drift velocities implies the spatial modulation of individual run-and-tumble random motions, and enables the bacterial population to migrate as a pushed wave front. Theoretical analysis and stochastic simulations further predicted that the pushed wave front can help a diverse population to stay in a tight group, while diverse individuals perform the same type of mean reverting processes around centers orderly aligned by their chemotactic abilities. This mechanism about the emergence of orderly collective migration from diverse individuals is experimentally demonstrated by titration of bacterial chemoreceptor abundance. These results reveal a simple computational principle for emergent ordered behaviors from heterogeneous individuals.