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Facial selectivity in mechanical bond formation: axially chiral enantiomers and geometric isomers from a simple prochiral macrocycle

Facial selectivity in mechanical bond formation: axially chiral enantiomers and geometric isomers from a simple prochiral macrocycle
Facial selectivity in mechanical bond formation: axially chiral enantiomers and geometric isomers from a simple prochiral macrocycle

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

0002-7863
9134-9141
Gallagher, Peter R.
021185c2-3c1d-4fa9-a36c-c51eb198c3ae
Savoini, Andrea
bd77b934-4427-414d-a80d-3b038c2c1ab6
Saady, Abed
fcdef21d-2f85-4740-bf09-0cfa775278cf
Maynard, John R.J.
4e09e766-1294-4056-8bff-4277874f0495
Butler, Patrick W.V.
6e0f7f4a-4cb5-4868-9820-d120c7d905f8
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Goldup, Stephen M.
0a93eedd-98bb-42c1-a963-e2815665e937
Gallagher, Peter R.
021185c2-3c1d-4fa9-a36c-c51eb198c3ae
Savoini, Andrea
bd77b934-4427-414d-a80d-3b038c2c1ab6
Saady, Abed
fcdef21d-2f85-4740-bf09-0cfa775278cf
Maynard, John R.J.
4e09e766-1294-4056-8bff-4277874f0495
Butler, Patrick W.V.
6e0f7f4a-4cb5-4868-9820-d120c7d905f8
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Goldup, Stephen M.
0a93eedd-98bb-42c1-a963-e2815665e937

Gallagher, Peter R., Savoini, Andrea, Saady, Abed, Maynard, John R.J., Butler, Patrick W.V., Tizzard, Graham J. and Goldup, Stephen M. (2024) Facial selectivity in mechanical bond formation: axially chiral enantiomers and geometric isomers from a simple prochiral macrocycle. Journal of the American Chemical Society, 146 (13), 9134-9141. (doi:10.1021/jacs.3c14329).

Record type: Article

Abstract

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

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More information

Accepted/In Press date: 14 February 2024
e-pub ahead of print date: 20 March 2024
Published date: 3 April 2024

Identifiers

Local EPrints ID: 489176
URI: http://eprints.soton.ac.uk/id/eprint/489176
ISSN: 0002-7863
PURE UUID: 42081993-d1e9-47ea-8511-5d1d0a92067b
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: 16 Apr 2024 16:43
Last modified: 21 May 2024 01:37

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Contributors

Author: Peter R. Gallagher
Author: Andrea Savoini
Author: Abed Saady
Author: John R.J. Maynard
Author: Patrick W.V. Butler

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