Enantioselective Tail-to-Head Terpene Cyclizations by Optically Active Hexameric Resorcin[4]arene Capsule Derivatives

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Mar 24

PMID 35324038

Authors

Daria Sokolova

GiovanniMaria Piccini

Konrad Tiefenbacher

Affiliations

Soon will be listed here.

Abstract

Molecular capsules enable the conversion of substrates inside a closed cavity, mimicking to some extent enzymatic catalysis. Chirality transfer from the molecular capsule onto the encapsulated substrate has been only studied in a few cases. Here we demonstrate that chirality transfer is possible inside a rather large molecular container of approximately 1400 Å . Specifically, we present 1) the first examples of optically active hexameric resorcin[4]arene capsules, 2) their ability to enantioselectively catalyze tail-to-head terpene cyclizations, and 3) the surprisingly high sensitivity of enantioselectivity on the structural modifications.

Citing Articles

The Versatile Applications of Calix[4]resorcinarene-Based Cavitands.

Wang K, Yan K, Liu Q, Wang Z, Hu X Molecules. 2025; 29(24.

PMID: 39769942 PMC: 11679249. DOI: 10.3390/molecules29245854.

Electric-Field Catalysis on Carbon Nanotubes in Electromicrofluidic Reactors: Monoterpene Cyclizations.

Jozeliunaite A, Guo S, Sakai N, Matile S Angew Chem Int Ed Engl. 2024; 64(4):e202417333.

PMID: 39387156 PMC: 11753599. DOI: 10.1002/anie.202417333.

Reactivity Inside Molecular Flasks: Acceleration Modes and Types of Selectivity Obtainable.

Syntrivanis L, Tiefenbacher K Angew Chem Int Ed Engl. 2024; 63(49):e202412622.

PMID: 39295476 PMC: 11586709. DOI: 10.1002/anie.202412622.

Sesquiterpene Cyclase BcBOT2 Promotes the Unprecedented Wagner-Meerwein Rearrangement of the Methoxy Group.

Moeller M, Dhar D, Drager G, Ozbasi M, Struwe H, Wildhagen M J Am Chem Soc. 2024; 146(26):17838-17846.

PMID: 38888422 PMC: 11228982. DOI: 10.1021/jacs.4c03386.

synthesis of inherently chiral heteracalix[4]aromatics from enantioselective macrocyclization enabled by chiral phosphoric acid-catalyzed intramolecular SAr reaction.

Li X, Cheng Y, Wang X, Tong S, Wang M Chem Sci. 2024; 15(10):3610-3615.

PMID: 38455024 PMC: 10915842. DOI: 10.1039/d3sc06436k.

References

Jongkind L, Caumes X, Hartendorp A, Reek J . Ligand Template Strategies for Catalyst Encapsulation. Acc Chem Res. 2018; 51(9):2115-2128. PMC: 6148444. DOI: 10.1021/acs.accounts.8b00345. View

Nakamura H, Ishihara K, Yamamoto H . Lewis acid-activated chiral leaving group: enantioselective electrophilic addition to prochiral olefins. J Org Chem. 2002; 67(15):5124-37. DOI: 10.1021/jo020165l. View

Katiyar A, Freire Sovierzoski J, Calio P, Vartia A, Thompson W . Water plays a dynamical role in a hydrogen-bonded, hexameric supramolecular assembly. Phys Chem Chem Phys. 2020; 22(11):6167-6175. DOI: 10.1039/c9cp06874k. View

Pluth M, Johnson D, Szigethy G, Davis A, Teat S, Oliver A . Structural consequences of anionic host-cationic guest interactions in a supramolecular assembly. Inorg Chem. 2008; 48(1):111-20. DOI: 10.1021/ic8012848. View

Mouarrawis V, Plessius R, van der Vlugt J, Reek J . Confinement Effects in Catalysis Using Well-Defined Materials and Cages. Front Chem. 2019; 6:623. PMC: 6308152. DOI: 10.3389/fchem.2018.00623. View

Brown C, Toste F, Bergman R, Raymond K . Supramolecular catalysis in metal-ligand cluster hosts. Chem Rev. 2015; 115(9):3012-35. DOI: 10.1021/cr4001226. View

Avram L, Cohen Y, Rebek Jr J . Recent advances in hydrogen-bonded hexameric encapsulation complexes. Chem Commun (Camb). 2011; 47(19):5368-75. DOI: 10.1039/c1cc10150a. View

Avram L, Cohen Y . Self-assembly of resorcin[4]arene in the presence of small alkylammonium guests in solution. Org Lett. 2008; 10(8):1505-8. DOI: 10.1021/ol702912u. View

Wang K, Jordan J, Hu X, Wang L . Supramolecular Strategies for Controlling Reactivity within Confined Nanospaces. Angew Chem Int Ed Engl. 2020; 59(33):13712-13721. DOI: 10.1002/anie.202000045. View

10.

Merget S, Catti L, Piccini G, Tiefenbacher K . Requirements for Terpene Cyclizations inside the Supramolecular Resorcinarene Capsule: Bound Water and Its Protonation Determine the Catalytic Activity. J Am Chem Soc. 2020; 142(9):4400-4410. DOI: 10.1021/jacs.9b13239. View

11.

Ueda Y, Ito H, Fujita D, Fujita M . Permeable Self-Assembled Molecular Containers for Catalyst Isolation Enabling Two-Step Cascade Reactions. J Am Chem Soc. 2017; 139(17):6090-6093. DOI: 10.1021/jacs.7b02745. View

12.

Brauer T, Zhang Q, Tiefenbacher K . Iminium Catalysis inside a Self-Assembled Supramolecular Capsule: Modulation of Enantiomeric Excess. Angew Chem Int Ed Engl. 2016; 55(27):7698-701. DOI: 10.1002/anie.201602382. View

13.

Takezawa H, Shitozawa K, Fujita M . Enhanced reactivity of twisted amides inside a molecular cage. Nat Chem. 2020; 12(6):574-578. DOI: 10.1038/s41557-020-0455-y. View

14.

Sokolova D, Piccini G, Tiefenbacher K . Enantioselective Tail-to-Head Terpene Cyclizations by Optically Active Hexameric Resorcin[4]arene Capsule Derivatives. Angew Chem Int Ed Engl. 2022; 61(25):e202203384. PMC: 9323437. DOI: 10.1002/anie.202203384. View

15.

Zarra S, Wood D, Roberts D, Nitschke J . Molecular containers in complex chemical systems. Chem Soc Rev. 2014; 44(2):419-32. DOI: 10.1039/c4cs00165f. View

16.

Nemat S, Tiefenbacher K . Thioderivatives of Resorcin[4]arene and Pyrogallol[4]arene: Are Thiols Tolerated in the Self-Assembly Process?. Org Lett. 2021; 23(17):6861-6865. DOI: 10.1021/acs.orglett.1c02426. View

17.

Garcia-Simon C, Gramage-Doria R, Raoufmoghaddam S, Parella T, Costas M, Ribas X . Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage. J Am Chem Soc. 2015; 137(7):2680-7. DOI: 10.1021/ja512637k. View

18.

Poole 3rd D, Mathew S, Reek J . Just Add Water: Modulating the Structure-Derived Acidity of Catalytic Hexameric Resorcinarene Capsules. J Am Chem Soc. 2021; 143(40):16419-16427. PMC: 8517980. DOI: 10.1021/jacs.1c04924. View

19.

Tan C, Chu D, Tang X, Liu Y, Xuan W, Cui Y . Supramolecular Coordination Cages for Asymmetric Catalysis. Chemistry. 2018; 25(3):662-672. DOI: 10.1002/chem.201802817. View

20.

Zhao C, Sun Q, Hart-Cooper W, DiPasquale A, Toste F, Bergman R . Chiral amide directed assembly of a diastereo- and enantiopure supramolecular host and its application to enantioselective catalysis of neutral substrates. J Am Chem Soc. 2013; 135(50):18802-5. DOI: 10.1021/ja411631v. View