Photocatalytic amidation and esterification with perfluoroalkyl iodide

Abstract

The successful generation of perfluoroalkyl radical (Rf) through photoredox catalysis has inspired us to investigate the preparation of various organolfuorine species. In this work, visible light-induced photocatalytic reactions for the...

Photocatalytic Aerobic Dehydrogenation of N-Heterocycles with Ir(III) Photosensitizers Bearing the 2(2′-Pyridyl)benzimidazole Scaffold

“… a Data for [1]PF 6 and [2]PF 6 reported by McCusker 53 and Ko, 54 respectively. Voltammograms recorded in acetonitrile solution (5 × 10 –4 M), using 0.1 M [ n Bu 4 N][PF 6 ] as supporting electrolyte with scan rate of 0.10 V·s –1 and referenced to Fc + /Fc (qr = quasi-reversible, ir = irreversible) b Δ E 1/2 = E 1/2 ox2 – E 1/2 red1 .…”

Photoredox Catalysis for the Fabrication of Water-Repellent Surfaces with Application for Oil/Water Separation

“…The product was purified by column chromatography with silica gel and characterized by IR, 1 H NMR, 19 F NMR, 13 C{ 1 H} NMR spectroscopy, mass spectrometry, and elemental analysis. An isolated yield of 20.5%, which is much lower than those for reactions for other substituted amines, 52,53 can be attributed to the silanization of the glassware and silica gel used in the reaction and purification. The purified product 1 shows a strong characteristic ν(CO) at 1691 cm −1 in the IR spectrum (Figure 1), similar to the related amide analogues reported in our previous research work.…”

“…Photoredox Catalysis of Perfluorooctyl Iodide with Aminoalkylsilane. To evaluate the applicability of our recently reported photocatalytic amidation 52,53 for surface functionalization, the reaction between trimethoxylsilyl-substituted amine (APTMS) and perfluorooctyl iodide (C 8 F 17 I) (Scheme 1a) was studied. The reaction gave the product of N- [3-(trihydroxylsilyl)propyl] perfluorooctanamide (1), indicating the hydrolysis of the methoxy groups during the photocatalytic reaction.…”

“…The purified product 1 shows a strong characteristic ν(CO) at 1691 cm −1 in the IR spectrum (Figure 1), similar to the related amide analogues reported in our previous research work. 52,53 The N-[3-(trihydroxysilyl)propyl] group can be characterized by 1 H NMR spectroscopy (Figure S2), whereas the perfluorooctamide moiety can be characterized by 19 F NMR spectroscopy (Figure S3). With 13 C{ 1 H} NMR spectroscopy (Figure S4), the C signals of both N- [3-(trihydroxylsily)propyl] and perfluorooctamide groups, as well as CO in the peptide linkage, have been characterized.…”

“…Silanization processes with fluoroalkyl-substituted silanes have been demonstrated to be useful for surface modification and the development of materials with advanced coatings. − However, the practical industrial applications of fluoroalkyl-substituted silanes in silanization processes are very limited due to its low reaction efficiencies in the silanization, the instability of these silanes for recovery/reuse, and the very high cost of fluoroalkyl-substituted silanes. With our recent work on photocatalytic fluoroalkylation using low-cost and readily accessible perfluoroalkyl iodides, − their successful applications for surface chemical functionalization would significantly reduce the cost of surface modification with fluoroalkyl functional moieties. Besides, photochemical surface modification together with a photomask enables the fabrication of patterned surfaces, which have many important applications. − Although the photocatalytic processes for surface modification with organofluorine compounds have not been reported, the feasibility of photocatalytic reactions for successful surface functionalization has been demonstrated.…”