Assemblies of 1,4-Bis(diarylamino)naphthalenes and Aromatic Amphiphiles: Highly Reducing Photoredox Catalysis in Water

Abstract

Host–guest assemblies of a designed 1,4-bis(diarylamino)naphthalene and V-shaped aromatic amphiphiles consisting of two pentamethylbenzene moieties bridged by an m-phenylene unit bearing two hydrophilic side chains emerged as highly reducing photoredox catalysis systems in water. An efficient demethoxylative hydrogen transfer of Weinreb amides has been developed. The present supramolecular strategy permits facile tuning of visible-light photoredox catalysis in water.

Key words

photoredox catalysis - supramolecular catalysts - organophotocatalysis - radical reaction - Weinreb amides - demethoxylation

Publication History

Received: 31 July 2021

Accepted after revision: 23 September 2021

Accepted Manuscript online:
23 September 2021

Article published online:
13 October 2021

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• 10 Photocatalytic Demethoxylation of Weinreb Amides: General Procedure A 4 mL sample bottle was charged with amide 4 (0.13 mmol), Et₃N (0.26 mmol), and 1.3 mM aq 3c (2 mL, 2 mol%), and then placed 1 cm away from blue LED lamps (λ = 425 nm). The mixture was irradiated, with stirring and cooling by a fan for 3–48 h. H₂O (5 mL) was then added and the resulting mixture was extracted with CH₂Cl₂ (3 × 15 mL). The organic layer was dried (Na₂SO₄) and concentrated, and the crude product was purified by gel-permeation chromatography. N,4-Dimethylbenzamide (5a) White solid; yield: 16.3 mg (88%, 0.109 mmol). ¹H NMR (400 MHz, CDCl₃): δ = 7.65 (d, J = 8.0 Hz, 2 H, Ar), 7.22 (d, J = 8.0 Hz, 2 H, Ar), 6.10 (br s, 1 H, NH), 3.00 (d, J = 4.7 Hz, 3 H, CH ₃), 2.39 (s, 3 H, CH ₃). N-Methylbiphenyl-4-carboxamide (5c) White solid; yield: 20.0 mg (69%, 0.0904 mmol). ¹H NMR (400 MHz, CDCl₃): δ = 7.84 (d, J = 8.3 Hz, 2 H, Ar), 7.65–7.59 (m, 4 H, Ar), 7.46 (dd, J = 7.1, 7.7 Hz, 2 H, Ar), 7.38 (t, J = 7.4 Hz, 1 H, Ar), 6.28 (br s, 1 H, NH), 3.04 (d, J = 4.8 Hz, 3 H, CH ₃).
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• 12 Quenching experiments for 3c with quenchers 4a and Et₃N in water showed a significant increase in fluorescence intensity. In addition, 4a affected the lifetime of the fluorescent excited species. These results also suggest that unique assemblies are formed in the present system (see the Supporting Information).