Covalent [2]Catenane and [2]Rotaxane Synthesis via a δ-Amino Acid Template

Abstract

Despite the advances in the synthesis of mechanically interlocked molecules, a generally applicable approach to interlocked natural products, such as lasso peptides, is yet to be formulated. While amino acid sequences have been introduced into several rotaxanes, the key structural components have always been dictated by the method used for supramolecular preorganization. In this work, we report the use of an ester-functionalized, aromatic δ-amino acid as the central covalent templating unit in the synthesis of both a [2]­catenane and a [2]­rotaxane from the same multimacrocyclic intermediate. This represents a key step toward future synthetic peptide-based interlocked products.

Distinctive features and challenges in catenane chemistry

“…MIM synthesis via a series of chemical transformations, in which a covalent scaffold with specifically oriented functional groups to favour entanglement formation is generated, is known as directed synthesis. 36 There are relatively less examples of catenanes synthesised by directed synthesis although the first few examples have been described in the 1960's. 36 a Recently, Itami and co-workers have reported the strategic use of a tetrahedral organosilicon to direct the formation and interlocking of hydrocarbon macrocycles into [2]catenanes and trefoil knots, and the topology of these nano-sized carbon materials is expected to have interesting effects on their physical, dynamic and optoelectrical properties ( Fig.…”

Rotaxane nanomachines in future molecular electronics

“…Many research studies about [2]rotaxane and its applications to moletronics have been reported. 52–166…”

Welcome to Volume 2 of ACS Organic & Inorganic Au

“…Over 2021, our content covered a range of exciting topics in all areas of organic and inorganic chemistry. These included the synthesis of a novel inorganic oxyfluoride, the development of new synthetic methods, − electrochemical transformations, visible-light-driven reactions, , polymerization, the synthesis of interlocked molecules, and the development of fluorescent probes . To celebrate the 2021 Nobel Prize in Chemistry awarded to Benjamin List and David MacMillan, we closed out 2021 by taking part in a joint Virtual Issue, “Asymmetric Organocatalysis: A Nobel Achievement”, with our sister ACS journals: Journal of the American Chemical Society , The Journal of Organic Chemistry , Accounts of Chemical Research , Chemical Reviews , Organic Letters , ACS Catalysis , Organic Process Research & Development , JACS Au , and Organometallics .…”