Challenges and Opportunities in the Post‐Synthetic Modification of Interlocked Molecules

Waelès, Philip; Gauthier, Maxime; Coutrot, Frédéric

doi:10.1002/ange.202007496

Cited by 11 publications

(4 citation statements)

References 134 publications

(100 reference statements)

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“…[33] To demonstrate the scalability of the methodology herein reported, the fluoroalkylation of DB24 C8 was carried out on a gram-scale affording 65 % (0,98 g) isolated yield of product 16 (see SI for details). The utility of the methodology is further highlighted by the post-synthetic fluoroalkylation of a mechanically interlocked molecule (MIM) [34] such as [2]rotaxane 20. Under the optimized reaction conditions and employing n-C 6 F 13 I as fluoroalkyl radical source, 50 % yield of monoperfluorohexylated [2]rotaxane 21 was obtained (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

Late‐Stage Photocatalytic Fluoroalkylation of Aromatic Crown Ethers in Aqueous Media

et al. 2023

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Modified crown ethers are fundamental building blocks in supramolecular chemistry, with applications in phase transfer catalysis, metal extraction, smart materials, and molecular machines. Here we report on a one-pot highly chemo-and regioselective photocatalytic fluoroalkylation protocol for the mono-functionalization of benzo substituted crown ethers. For this important class of macrocycles, the method described here represents one of the few late-stage functionalization procedures that is both high yielding and scalable. Because of its breadth of scope and substrate tolerance, the devised approach can be applied to a wide range of aromatic crown ethers (18 examples, up to 99 % yield), including those engaged in mechanically interlocked molecules.

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Section: Resultsmentioning

confidence: 99%

Late‐Stage Photocatalytic Fluoroalkylation of Aromatic Crown Ethers in Aqueous Media

et al. 2023

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“…In our design strategy, inspired by recent developments in post-synthetic modification of rotaxanes [35][36][37][38][39] , a wheel assembling approach is proposed for the efficient, precise, and diverse synthesis of both sequence isomers of hetero [3]rotaxanes. First, to shorten the synthetic routes and improve the synthetic efficiency, a [2]rotaxane with exchangeable stoppers is employed as the key precursor.…”

Section: General Design Strategy and The Preparation Of Key [2]rotaxa...mentioning

confidence: 99%

Sequence Matters: Precise Synthesis of Hetero[3]rotaxane Isomers with Sequence-dependent Chemical Reactivity and Circularly Polarized Luminescence

Peng

Jia

Wang

et al. 2023

Preprint

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Sequence isomerism plays fundamental roles in the encoding of biological information and in tuning material performance, but engineering sequences and elucidating their effects remain a major and largely unmet challenge in synthetic chemistry. Herein, We develop a novel wheel assembling approach aiming at the precise sequence control of hetero[3]rotaxanes, a typical family of mechanically interlocked molecules. Based on a key [2]rotaxane precursor with exchangeable pentafluorophenyl ester stoppers, We successfully synthesized both sequence isomers of diverse hetero[3]rotaxanes. Moreover, taking advantage of the chirality retention along with the wheel assembling process, corresponding sequence isomers of chiral functionalized hetero[3]rotaxanes were further precisely synthesized. Impressively, these hetero[3]rotaxanes revealed remarkable sequence-dependent chemical reactivity and circularly polarized luminescence, highlighting fantastic sequence effects. This proof-of-concept study lays the foundation for the investigations on the structure-property relationships of heterorotaxanes, which would further direct the rational design and precise synthesis of sequence-defined heterorotaxanes with desired properties for practical use.

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“…The reactions shown in Scheme 1 are probably the only two examples known of diastereoselective post‐synthetic modification of the achiral thread carried out under the chiral influence of the ring, with axially chiral binaphtyl units, in a [2]rotaxane [42, 43] In this manuscript we disclose our results on approaching a similar strategy by using another type of stereogenic inductor, point chirality ( only a single chiral carbon atom ! ), placed at the macrocycle of a [2]rotaxane, and a different diastereoselective transformation occurring at the thread.…”

Section: Introductionmentioning

confidence: 99%

Ring‐to‐Thread Chirality Transfer in [2]Rotaxanes for the Synthesis of Enantioenriched Lactams

et al. 2022

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The synthesis of chiral mechanically interlocked molecules has attracted a lot of attention in the last few years, with applications in different fields, such as asymmetric catalysis or sensing. Herein we describe the synthesis of orientational mechanostereoisomers, which include a benzylic amide macrocycle with a stereogenic center, and nonsymmetric N-(arylmethyl)fumaramides as the axis. The base-promoted cyclization of the initial fumaramide thread allows enantioenriched value-added compounds, such as lactams of different ring sizes and amino acids, to be obtained. The chiral information is effectively transmitted across the mechanical bond from the encircling ring to the interlocked lactam. High levels of enantioselectivity and full control of the regioselectivity of the final cyclic compounds are attained.

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Challenges and Opportunities in the Post‐Synthetic Modification of Interlocked Molecules

Abstract: Scheme 6. Amidation-based stopper exchange of a[2]rotaxane containing a2,6-diphenyl-4-nitrophenyle ster:achemical route to agalactoenkephalin [2]rotaxane. Scheme 5. Amidation-based stopper exchange of DCC-[2]rotaxanes.

Cited by 11 publications

References 134 publications

Late‐Stage Photocatalytic Fluoroalkylation of Aromatic Crown Ethers in Aqueous Media

Late‐Stage Photocatalytic Fluoroalkylation of Aromatic Crown Ethers in Aqueous Media

Sequence Matters: Precise Synthesis of Hetero[3]rotaxane Isomers with Sequence-dependent Chemical Reactivity and Circularly Polarized Luminescence

Ring‐to‐Thread Chirality Transfer in [2]Rotaxanes for the Synthesis of Enantioenriched Lactams

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