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A chiral interlocking auxiliary strategy for the synthesis of mechanically planar chiral rotaxanes

A chiral interlocking auxiliary strategy for the synthesis of mechanically planar chiral rotaxanes
A chiral interlocking auxiliary strategy for the synthesis of mechanically planar chiral rotaxanes
Rotaxanes can display molecular chirality solely due to the mechanical bond between the axle and encircling macrocycle without the presence of covalent stereogenic units. However, the synthesis of such molecules remains challenging. We have discovered a combination of reaction partners that function as a chiral interlocking auxiliary to both orientate a macrocycle and, effectively, load it onto a new axle. Here we use these substrates to demonstrate the potential of a chiral interlocking auxiliary strategy for the synthesis of mechanically planar chiral rotaxanes by producing examples in high enantiopurity (93–99% e.e.), including so-called 'impossible' rotaxanes whose axles lack any functional groups that would allow their direct synthesis by other means. Intriguingly, by varying the order of bond-forming steps, we can effectively choose which end of an axle the macrocycle is loaded onto, enabling the synthesis of both hands of a single target using the same reactions and building blocks.
1755-4330
De Juan garrudo, Alberto
3d94d634-c39b-46c7-a06a-d701bec139de
Lozano Mena, David
bb8bd345-aaae-4e61-92d0-3da392e83a8f
Heard, Andrew, William
f01893de-d170-48db-8804-b0a83bc4f192
Jinks, Michael A
c8ce33cc-8ead-4763-b294-ae94ce0475d0
Meijide Suarez, Jorge
8a280801-225d-4d11-b0e3-4f34ceca819c
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Goldup, Stephen M.
0a93eedd-98bb-42c1-a963-e2815665e937
De Juan garrudo, Alberto
3d94d634-c39b-46c7-a06a-d701bec139de
Lozano Mena, David
bb8bd345-aaae-4e61-92d0-3da392e83a8f
Heard, Andrew, William
f01893de-d170-48db-8804-b0a83bc4f192
Jinks, Michael A
c8ce33cc-8ead-4763-b294-ae94ce0475d0
Meijide Suarez, Jorge
8a280801-225d-4d11-b0e3-4f34ceca819c
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Goldup, Stephen M.
0a93eedd-98bb-42c1-a963-e2815665e937

De Juan garrudo, Alberto, Lozano Mena, David, Heard, Andrew, William, Jinks, Michael A, Meijide Suarez, Jorge, Tizzard, Graham J. and Goldup, Stephen M. (2021) A chiral interlocking auxiliary strategy for the synthesis of mechanically planar chiral rotaxanes. Nature Chemistry. (doi:10.26434/chemrxiv.13553996.v2). (In Press)

Record type: Article

Abstract

Rotaxanes can display molecular chirality solely due to the mechanical bond between the axle and encircling macrocycle without the presence of covalent stereogenic units. However, the synthesis of such molecules remains challenging. We have discovered a combination of reaction partners that function as a chiral interlocking auxiliary to both orientate a macrocycle and, effectively, load it onto a new axle. Here we use these substrates to demonstrate the potential of a chiral interlocking auxiliary strategy for the synthesis of mechanically planar chiral rotaxanes by producing examples in high enantiopurity (93–99% e.e.), including so-called 'impossible' rotaxanes whose axles lack any functional groups that would allow their direct synthesis by other means. Intriguingly, by varying the order of bond-forming steps, we can effectively choose which end of an axle the macrocycle is loaded onto, enabling the synthesis of both hands of a single target using the same reactions and building blocks.

Text
rvsd2 MS de Juan Shuttle Synthesis clean - Accepted Manuscript
Restricted to Repository staff only until 17 March 2022.
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Accepted/In Press date: 20 July 2021

Identifiers

Local EPrints ID: 451152
URI: http://eprints.soton.ac.uk/id/eprint/451152
ISSN: 1755-4330
PURE UUID: 4a0f0c1a-c118-4a97-8375-59267cd25501
ORCID for Graham J. Tizzard: ORCID iD orcid.org/0000-0002-1577-5779
ORCID for Stephen M. Goldup: ORCID iD orcid.org/0000-0003-3781-0464

Catalogue record

Date deposited: 14 Sep 2021 15:26
Last modified: 15 Sep 2021 02:03

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Contributors

Author: Alberto De Juan garrudo
Author: David Lozano Mena
Author: Andrew, William Heard
Author: Michael A Jinks
Author: Jorge Meijide Suarez

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