Facial Selectivity in Mechanical Bond Formation: Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle

Peter Gallagher; Andrea Savoini; Abed Saady; John R.J. Maynard; Patrick Butler; Graham J. Tizzard; Stephen Goldup

doi:10.1021/jacs.3c14329

Facial Selectivity in Mechanical Bond Formation: Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle

Peter Gallagher, Andrea Savoini, Abed Saady, John R.J. Maynard, Patrick Butler, Graham J. Tizzard, Stephen Goldup^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Journal	Journal of the American Chemical Society
Early online date	20 Mar 2024
DOIs	https://doi.org/10.1021/jacs.3c14329
Publication status	E-pub ahead of print - 20 Mar 2024

Bibliographical note

Funding:
H2020 European Research Council (724987), Royal Society (RSWF\FT\180010).

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10.1021/jacs.3c14329Licence: Creative Commons: Attribution (CC BY)

GallagherPR2024FacialFinal published version, 2.87 MBLicence: Creative Commons: Attribution (CC BY)

Research data supporting the publication "Facial Selectivity in Mechanical Bond Formation: Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle"
Goldup, S. (Creator), University of Birmingham, 18 Mar 2024
DOI: https://doi.org/10.25500/edata.bham.00001077
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Cite this

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title = "Facial Selectivity in Mechanical Bond Formation: Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle",

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.",

author = "Peter Gallagher and Andrea Savoini and Abed Saady and Maynard, {John R.J.} and Patrick Butler and Tizzard, {Graham J.} and Stephen Goldup",

note = "Funding: H2020 European Research Council (724987), Royal Society (RSWF\FT\180010).",

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doi = "10.1021/jacs.3c14329",

language = "English",

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T2 - Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle

AU - Gallagher, Peter

AU - Savoini, Andrea

AU - Saady, Abed

AU - Maynard, John R.J.

AU - Butler, Patrick

AU - Tizzard, Graham J.

AU - Goldup, Stephen

N1 - Funding: H2020 European Research Council (724987), Royal Society (RSWF\FT\180010).

PY - 2024/3/20

Y1 - 2024/3/20

N2 - 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.

AB - 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.

U2 - 10.1021/jacs.3c14329

DO - 10.1021/jacs.3c14329

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

Facial Selectivity in Mechanical Bond Formation: Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle

Abstract

Bibliographical note

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Research data supporting the publication "Facial Selectivity in Mechanical Bond Formation: Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle"

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