1.
2.
Frisch, H. L. & Wasserman, E. Chemical topology. J. Am. Chem. Soc. 83,
3789–3795 (1961).
Schill, G. Catenanes, Rotaxanes and Knots (Academic Press, New York, 1971).
NATURE COMMUNICATIONS | (2021)12:404 | https://doi.org/10.1038/s41467-020-20372-0 | www.nature.com/naturecommunications
A Self-archived copy in
Kyoto University Research Information Repository
https://repository.kulib.kyoto-u.ac.jp
NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-20372-0
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
Kaida, Y., Okamoto, Y., Chambron, J.-C., Mitchell, D. K. & Sauvage, J.-P. The
separation of optically active copper (I) catenates. Tetrahedron Lett. 34,
1019–1022 (1993).
Yamamoto, C., Okamoto, Y., Schmidt, T., Jager, R. & Vögtle, F. Enantiomeric
resolution of cycloenantiomeric rotaxane, topologically chiral catenane, and
pretzel-shaped molecules: observation of pronounced circular dichroism. J.
Am. Chem. Soc. 119, 10547–10548 (1997).
Bruns, C. J. & Stoddart, J. F. The Nature of the Mechanical Bond: from
Molecules to Machines (John Wiley & Sons, Inc., 2016).
Jamieson, E. M. G., Modicom, F. & Goldup, S. M. Chirality in rotaxanes and
catenanes. Chem. Soc. Rev. 47, 5266–5311 (2018).
Leigh, D. A., Marcos, V. & Wilson, M. R. Rotaxane catalysts. ACS Catal. 4,
4490–4407 (2014).
Heard, A. W. & Goldup, S. M. Synthesis of a mechanically planar chiral
rotaxane ligand for enantioselective catalysis. Chem. 6, 994–1006 (2020).
Martinez-Cuezva, A., Saura-Sanmartin, A., Alajarin, M. & Berna, J.
Mechanically interlocked catalysts for asymmetric synthesis. ACS Catal. 10,
7719–7733 (2020).
Erbas-Cakmak, S., Leigh, D. A., McTernan, C. T. & Nussbaumer, A. L.
Artificial molecular machines. Chem. Rev. 115, 10081–10206 (2015).
Evans, N. H. Chiral catenanes and rotaxanes: fundamentals and emerging
applications. Chem. Eur. J. 24, 3101–3112 (2018).
Pairault, N. & Niemeyer, J. Chiral mechanically interlocked moleculesApplications of rotaxanes, catenates and molecular knots in stereoselective
chemosensing and catalysis. Synlett 29, 689–698 (2018).
Nakazono, K. & Takata, T. Mechanical chirality of rotaxanes: synthesis and
function. Symmetry 12, 144 (2020).
Maynard, J. R.-J.- & Goldup, S. M. Strategies for the synthesis of enantiopure
mechanically chiral molecules. Chem 6, 1914–1932 (2020).
Bordoli, R. J. & Goldup, S. M. An efficient approach to mechanically planar
chiral rotaxanes. J. Am. Chem. Soc. 136, 4817–4820 (2014).
Jinks, M. A. et al. Stereoselective synthesis of mechanically planar rotaxanes.
Angew. Chem. Int. Ed. 57, 14806–14810 (2018).
Denis, M., Lewis, J. E. M., Modicom, F. & Goldup, S. M. An auxiliary
approach for the stereoselective synthesis of topologically chiral catenanes.
Chem 5, 1512–1520 (2019).
Mikata, Y. et al. Catalytic asymmetric synthesis and optical resolution of
planar chiral rotaxane. Chem. Lett. 36, 162–163 (2007).
Tian, C., Fielden, S. D. P., Pérez-Saavedra, B., Vitorica-Yrezabal, I. J. & Leigh,
A. D. Single-step enantioselective synthesis of mechanically planar chiral [2]
rotaxanes using a chiral leaving group strategy. J. Am. Chem. Soc. 142,
9803–9808 (2020).
Keith, J. M., Larrow, J. F. & Jacobsen, E. N. Practical considerations in kinetic
resolution reactions. Adv. Syn. Catal. 343, 5–26 (2001).
List, B. (ed.) Science of Synthesis, Asymmetric Organocatalysis 1, Lewis Base
and Acid Catalysts (Thieme, Stuttgart, New York, 2012).
Lewis, C. A. et al. Remote desymmetrization at near-nanometer group
separation catalyzed by a miniaturized enzyme mimic. J. Am. Chem. Soc. 128,
16454–17455 (2006).
Alvarez-Pérez, M., Goldup, S. M., Leigh, D. A. & Slawin, A. M. Z. A
chemically-driven molecular information ratchet. J. Am. Chem. Soc. 130,
1836–1838 (2008).
Yoshida, K., Shigeta, T., Furuta, T. & Kawabata, T. Catalyst-controlled reversal
of chemoselectivity in acylation of 2-aminopentane-1,5-diol derivatives. Chem.
Commun. 48, 6981–6983 (2012).
Yoshida, K. et al. Non-enzymatic geometry-selective acylation of tri- and
tetrasubstituted α,α’-alkenediols. Adv. Syn. Catal. 354, 3291–3298 (2012).
Yamanaka, M. et al. Origin of high E-selectivity in 4-pyrrolidinopyridinecatalyzed tetrasubstituted α,α’-alkenediol: a computational and experimental
study. J. Org. Chem. 80, 3075–3082 (2015).
Imayoshi, A. et al. Insights into the molecular recognition process in
organocatalytic chemoselective monoacylation of 1,5-pentanediol. Adv. Synth.
Catal. 358, 1337–1344 (2016).
Kawabata, T., Nagato, M., Takasu, K. & Fuji, K. Nonenzymatic kinetic
resolution of racemic alcohols through an “induced fit” process. J. Am. Chem.
Soc. 119, 3169–3170 (1997).
Schedel, H. et al. Asymmetric desymmetrization of meso-diols by C2symmetric chiral 4-pyrrolidinopyridines. Beistein. J. Org. Chem. 8, 1778–1787
(2012).
Tachibana, Y., Kawasaki, H., Kihara, N. & Takata, T. Sequential O- and Nacylation protocol for high-yield preparation and modification of rotaxanes:
31.
32.
33.
34.
35.
36.
37.
ARTICLE
synthesis, functionalization, structure, and intercomponent interaction of
rotaxanes. J. Org. Chem. 71, 5093–5104 (2006).
Kawabata, T., Muramatsu, W., Nishio, T., Shibata, T. & Schedel, H. A catalytic
one-step process for the chemo- and regioselective acylation of
monosaccharides. J. Am. Chem. Soc. 129, 12890–12895 (2007).
Yanagi, M., Imayoshi, A., Ueda, Y., Furuta, T. & Kawabata, T. Carboxylate
anions accelerate pyrrolidinopyridine (ppy)-catalyzed acylation: Catalytic siteselective acylation of a carbohydrate by in situ counteranion exchange. Org.
Lett. 19, 3099–3102 (2017).
Birman, V. B. & Li, X. M. Benzotetramisole: a remarkably enantioselective acyl
transfer catalyst. Org. Lett. 8, 1351–1354 (2006).
Yoshida, K., Furuta, T. & Kawabata, T. Organocatalytic chemoselective
monoacylation of 1,n-linear diols. Angew. Chem. Int. Ed. 50, 4888–4892
(2011).
Hara, K. et al. Influence of novel supramolecular substance, [2]rotaxane, on
the caspase signaling pathway in melanoma and colon cancer cells in vitro. J.
Pharm. Sci. 122, 153–157 (2013).
Fujita, Y. et al. Characterization of the cytotoxic activity of [2]rotaxane (TROA0001), a novel supramolecular compound, in cancer cells. Arch. Pharm. Res.
39, 825–832 (2016).
Barat, R. et al. A mechanically interlocked molecular system programed for
the delivery of an anticancer drug. Chem. Sci. 6, 2608–2613 (2015).
Acknowledgements
This research was financially supported by Grants-in-Aids for Scientific Research (S)
(JP26221301), Young Scientists (B) (JP15K18827), and Scientific Research on Innovative
Areas “Advanced Molecular Transformations by Organocatalysts” (JP23105008) and
“Middle Molecular Strategy” (JP16H01148). A.I. acknowledges the financial support
through JSPS Research Fellowships for Young Scientists (JP15J10954).
Author contributions
T.K. conceived the work; A.I., B.V.L., and T.K. devised the experiments; A.I. carried out
the major part of the experiments; B.V.L., Y.U., and A.M. carried out the experiments;
Y.U., T.Y., and T.F. supported analyses of data; Y.U. performed the computational study;
A.I. and T.K. wrote the paper.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information is available for this paper at https://doi.org/10.1038/s41467020-20372-0.
Correspondence and requests for materials should be addressed to T.K.
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