Photoswitchable Interlocked Thiodiglycolamide As a Cocatalyst of a Chalcogeno-Baylis-Hillman Reaction

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2017 Jun 6

PMID 28580109

Citations 23

Authors

Alberto Martinez-Cuezva

Adrian Saura-Sanmartin

Tomas Nicolas-Garcia

Cristian Navarro

Raul-Angel Orenes

Mateo Alajarin

Jose Berna

Affiliations

Soon will be listed here.

Abstract

En route to a photoswitchable interlocked catalyst we have proved the ability of thiodiglycolamide to act as a template in the formation of hydrogen-bonded [2]rotaxanes. X-ray diffraction studies reveal the shielding of the sulfide atom by the macrocycle. A series of molecular shuttles are described as having an isomerizable fumaramide and thiodiglycolamide binding sites for controlling the relative ring position at will. By employing these systems as photoregulated catalysts, the TiCl-mediated chalcogeno-Morita-Baylis-Hillman reaction is tested. In the presence of the maleamide shuttle, in which the sulfide function is encapsulated by the macrocycle, a complete loss in control of the geometry of the produced aldol is observed. The -aldol adduct is predominantly obtained when the photoisomerized fumaramide shuttle, in which the sulfide function is exposed, is used.

Citing Articles

Mechanical insulation of aza-Pechmann dyes within [2]rotaxanes.

Cutillas-Font G, Pastor A, Alajarin M, Martinez-Cuezva A, Marin-Luna M, Batanero B Chem Sci. 2024; 15(34):13823-13831.

PMID: 39211492 PMC: 11352530. DOI: 10.1039/d4sc03657c.

Conjugated bis(enaminones) as effective templates for rotaxane assembly and their post-synthetic modifications.

Razi S, Marin-Luna M, Alajarin M, Martinez-Cuezva A, Berna J Commun Chem. 2024; 7(1):170.

PMID: 39098851 PMC: 11298525. DOI: 10.1038/s42004-024-01258-4.

Photoswitchable Catalysis by a Self-Assembled Molecular Cage.

DiNardi R, Rasheed S, Capomolla S, Chak M, Middleton I, Macreadie L J Am Chem Soc. 2024; 146(31):21196-21202.

PMID: 39051845 PMC: 11311219. DOI: 10.1021/jacs.4c04846.

Urea-Based [2]Rotaxanes as Effective Phase-Transfer Organocatalysts: Hydrogen-Bonding Cooperative Activation Enabled by the Mechanical Bond.

Puigcerver J, Zamora-Gallego J, Marin-Luna M, Martinez-Cuezva A, Berna J J Am Chem Soc. 2024; 146(33):22887-22892.

PMID: 38975636 PMC: 11345763. DOI: 10.1021/jacs.4c06630.

Kinetically controlled synthesis of rotaxane geometric isomers.

McCarthy D, Xu K, Schenkelberg M, Balegamire N, Liang H, Bellino S Chem Sci. 2024; 15(13):4860-4870.

PMID: 38550687 PMC: 10967009. DOI: 10.1039/d3sc04412b.

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