Sulphonic acid functionalized porphyrin anchored with a meso-substituted triazolium ionic liquid moiety: a heterogeneous photo-catalyst for metal/base free C–C cross-coupling and C–N/C–H activation using aryl chloride under visible light irradiation

Abstract

We report an easy process to synthesize sulphonic acid functionalized porphyrin, anchored with meso-substituted triazolium ionic liquid moiety (SAFPTILM) for metal/base free C-C cross-coupling and C-N/C-H activation using aryl chloride...

Visible‐Light Aided C−H activation: Metal/Base‐Free Generation of C−C bonds using Porphyrin Photocatalyst

“…The computational study also revealed that the lowest energy frontier HOMO with the energy of −8.07 eV is located at the para position of the aniline [47] . A similar protocol on Benzidine synthesis using chloro‐aniline and metal‐free photocatalyst (Ullman homo coupling reaction) has been successfully attempted by our group and has appeared in the publication [48] . Based on the optimized reaction conditions, we successfully experimented overall pertinency of heterogenous CPDCFBM photocatalyst for C−H activation reactions between a few aromatic compounds (alpha and beta naphthol) and unsubstituted or substituted aryl halides with electron‐donating and withdrawing groups (Table 2, compound 1 – 11 ).…”

“…[47] A similar protocol on Benzidine synthesis using chloro-aniline and metal-free photocatalyst (Ullman homo coupling reaction) has been successfully attempted by our group and has appeared in the publication. [48] Based on the optimized reaction conditions, we successfully experimented overall pertinency of heterogenous CPDCFBM photocatalyst for CÀ H activation reactions between a few aromatic compounds (alpha and beta naphthol) and unsubstituted or substituted aryl halides with electron-donating and withdrawing groups (Table 2, compound 1-11). The metal-free CPDCFBM photocatalyst endured various functional groups attached to aryl halides such as NO 2 , NH 2 , CHO, Cl and OH and exhibited better yields of over 80 % except for the reaction between α-naphthol and 4-fluorobenzaldehyde, which yields 69 % product (Table 2, compound 11), the lowering of the yield can be accounted based on the stronger bond between carbon and fluorine.For all these reactions (Table 2, compound 1-11), a preferential activation at ortho-position with respect to substituents (À OH) on aromatic compounds (alpha or beta naphthol) has been observed.…”

A Metal/Solvent/Additive Free Compliant Route to Ullmann‐Type C−N Coupling using Ionic Liquid Entangled Porphyrin Heterogeneous Photocatalyst

“…In a typical synthesis, a mixture of 4‐chlorobenzaldehyde 2.81 g (20 mmol) and phthalonitrile 2.56 g (20 mmol) in acetonitrile (30 mL) was irradiated under with 5 W LED in a homemade photoreactor for 24 h at room temperature [50] . (Scheme 5).…”

Solvent/metal-free benzimidazolium-based carboxyl-functionalized porphyrin photocatalysts for the room-temperature alkylation of amines under the irradiation of visible light

“…In the previous contribution in photocatalysis, we have established a sulphonic acid-functionalized porphyrin@-meso-substituted triazolium ionic liquid moiety as a heterogeneous photocatalyst for C-C/C-N bond formation and C-H activation reactions in the presence of LED light. 52 In this study, we obtained and characterized metalfree benzimidazolium-based carboxyl-functionalized porphyrin (MFBBCFPc) as a heterogeneous photocatalyst. MFBBCFPc is used as a photocatalyst for the first time for the N-alkylation of primary/secondary amines with various alcohols under visible light irradiation (5 W LED) using a homemade photoreactor (Scheme 1).…”