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 a range of examples with 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. [Figure not available: see fulltext.]
Original language | English |
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Pages (from-to) | 179-187 |
Number of pages | 9 |
Journal | Nature Chemistry |
Volume | 14 |
Issue number | 2 |
Early online date | 29 Nov 2021 |
DOIs | |
Publication status | Published - Feb 2022 |
Bibliographical note
Funding Information:S.M.G. thanks the European Research Council (Consolidator Grant Agreement number 724987), the EPSRC (EP/L016621/1) and the Leverhulme Trust (ORPG-2733) for funding and the Royal Society for a Wolfson Research Fellowship (RSWF\FT\180010). J.M.S. thanks the Royal Society for a Newton International Fellowship (NIF\R1\181686). A.W.H. thanks the University of Southampton for a Presidential Scholarship.
Publisher Copyright:
© 2021, The Author(s), under exclusive licence to Springer Nature Limited.
ASJC Scopus subject areas
- General Chemistry
- General Chemical Engineering