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 stereo-differentiating interaction sufficient for reasonable stereoselectivity. Using this understanding, we were able to demonstrate the first direct enantioselective (70% ee) synthesis of a mechanically axially chiral rotaxane..
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Preprint| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
chemRxiv.org - (2023) vom: 18. Dez. Zur Gesamtaufnahme - year:2023 |
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| Sprache: |
Englisch |
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| Beteiligte Personen: |
Savoini, Andrea [VerfasserIn] |
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| Links: |
Volltext [kostenfrei] |
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| doi: |
10.26434/chemrxiv-2023-60b2b-v2 |
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| 520 | |a 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 stereo-differentiating interaction sufficient for reasonable stereoselectivity. Using this understanding, we were able to demonstrate the first direct enantioselective (70% ee) synthesis of a mechanically axially chiral rotaxane. | ||
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