Induction of molecular asymmetry by a remote chiral group

Mechanical transduction via a single soft polymer

“…The results of this study show that controlling the orienta- positioning, work, force, information, control, and molecular agents. This unified mechanism covers a wide range of applications, including transduction of mechanical actions (biased positioning, work, force) in molecular motors or simpler nanoactuators [24], remote point-to-point control [25,26] (e.g., via the polymer-transduced force and positioning), information relay [27,28] or signal transduction, site-specific delivery of molecules [29] (e.g., in nanoassembly lines [53]), sensing (e.g., by site-specifically concentrating target molecules for higher detection sensitivity), and sorting of molecular cargos (e.g., on nanorobotic platforms [54]).…”

“…These applications mostly have been demonstrated experimentally using other mechanisms, including steric hindrance [27,28] between closely packaged neighbors, chemical mechanisms [9,18,25,26,55] that inflict permanent changes to prevent repeatable operation, or by random intramolecular diffusion [29], etc. The orientation-based transduction is an alternative mechanism for actively controlled, repeatable, and long-range operation.…”

“…Soft polymers are also used in nonmotor applications to transmit mechanical actions, control, information, and molecular agents from one location to another. Examples include mechanical transduction via polymer brushes, collectively [24], remote asymmetric control [25,26] through a single flexible molecular linker for the purpose of chemical synthesis, distant intramolecular relay of information [27,28] based on steric hindrance between nearest neighbors, and site-specific delivery of molecules [29] by a swinging polymer immobilized at one end.…”

Point‐to‐Point Ultra‐Remote Asymmetric Control with Flexible Linker

“…Diastereoselectivity in intramolecular asymmetric inductions at more than a few bonds from a stereogenic center is very rare. The conventional exceptions require either the formation of rigid cyclic structures to communicate the stereo signal, the conformational orientation of the linkage by a supramolecular method or the relay of the system by a proximate asymmetric induction including hydrogen‐bond foldamer…”

“…[1] Diastereoselectivity in intramolecular asymmetric inductions at more than af ew bonds from as tereogenic centeri sv ery rare. The conventional exceptions [2] requiree ither the formationo fr igid cyclics tructures to communicate the stereo signal, [3] the conformational orientation of the linkage [4] by as upramolecular method [5] or the relay of the system by ap roximate asymmetric induction including hydrogen-bond foldamer. [6] Here, we show ap oint-to-point ultra-remotei ntramolecular asymmetrici nduction through 38 bonds (1,39-induction) by using the principle of direct orientation of catalytic and reactive moieties in asymmetric addition of iPr 2 Zn to pyrimidine-5carbaldehyde.…”