Mechanical stereochemistry arises when the interlocking of stereochemically trivial covalent subcomponents results in a complex object. Although this general concept was identified 1961, stereochemical description these molecules is still under development to extent that new forms mechanical are being identified. Here, we present simple analysis rotaxane and catenane allowed us identify final missing stereogenic unit, an overlooked form geometric isomerism, demonstrate its stereoselective synthesis.

In 1971, Schill recognized that a prochiral macrocycle encircling an oriented axle led to geometric isomerism in rotaxanes. More recently, we identified overlooked chiral stereogenic unit rotaxanes arises when encircles axle. Here, show both units can be accessed using equivalent strategies, with single weak stereodifferentiating interaction sufficient for moderate excellent stereoselectivity. Using this understanding, demonstrated the first direct enantioselective (70% ee) synthesis of...

In 1971, Schill recognized that a prochiral macrocycle encircling an oriented axle led to geometric isomerism in rotaxanes. More recently, we identified overlooked chiral stereogenic unit rotaxanes arises when encircles axle. Here show both units can be accessed using equivalent strategies, with single weak stereo-differentiating interaction sufficient for reasonable stereoselectivity. Using this understanding, were able demonstrate the first direct enantioselective (70% ee) synthesis of...

Mechanical geometric isomerism, which arises when bilaterally dissymmetric components are interlocked such that their internal mirror planes can be made congruent, is under-explored using simple prochiral components. Here we demonstrate a single intercomponent H-bond appears sufficient to control the formation of rotaxanes and catenanes containing canonical mechanical stereochemistry identify new stereogenic unit rotaxanes, yielded shuttling auxiliary synthesis.

The chiral mechanical axial stereogenic unit of rotaxanes was only recently recognized, despite equivalent mechanically axially catenanes being discussed in the early 1960s. Here we demonstrate that a single H-bond between groups differentiate faces macrocycle and axle appears sufficient to deliver high diastereocontrol (80% de) bond forming step extend this observation first direct enantioselective approach up 70% ee.

Mechanical stereochemistry arises when the interlocking of stereochemically trivial covalent subcomponents results in a stereochemical complex object. Although this general concept was identified 1961, description these molecules is still under development, with new mechanical stereoisomers recently. Here we present simple analysis rotaxane and catenane that allowed us to identify final missing stereogenic unit, an overlooked form geometric isomerism, demonstrate its stereoselective synthesis.

Abstract The term chiral was introduced by Lord Kelvin over a century ago to describe objects that are distinct from their own mirror image. Chirality is relevant in many scientific areas, but particularly chemistry because different image forms of molecule famously have biological properties. typically arises molecules due rigidly arrangement covalently bonded atoms. Less generally appreciated molecular chirality can arise when threaded through one another create mechanical bond. For...

Chirality, the property of objects that are distinct from their own mirror image, is important in many scientific areas but particularly chemistry, where appearance molecular chirality because rigid arrangements atoms space famously influences a molecule’s biological properties. Less generally appreciated two rings with chemically faces combined like links chain results chiral structure even when achiral. To date, no enantiopure examples such mechanically axially catenanes has been reported....

Chirality, the property of objects that are distinct from their own mirror image, is important in many scientific areas but particularly chemistry, where appearance molecular chirality because rigid arrangements atoms space famously influences a molecule’s biological properties. Less generally appreciated two rings with chemically faces combined like links chain results chiral structure even when achiral. To date, no enantiopure examples such mechanically axially catenanes has been reported....

Chirality, the property of objects that are distinct from their own mirror image, is important in many scientific areas but particularly chemistry, where appearance molecular chirality because rigid arrangements atoms space famously influences a molecule’s biological properties. Less generally appreciated two rings with chemically faces combined like links chain results chiral structure even when achiral. To date, no enantiopure examples such mechanically axially catenanes has been reported....