Facile, One‐Step Synthesis of 5‐Substituted Thieno[3,4‐c]pyrrole‐4,6‐dione by Palladium‐Catalyzed Carbonylative Amidation

Abstract

Described herein is a facile, one‐step synthesis of 5‐substituted thieno[3,4‐c]pyrrole‐4,6‐diones (TPDs) by a palladium‐catalyzed carbonylative amidation of commercially available dibromoaryl compounds under mild conditions. TPDs are important structural components for organic electronics. Our optimal conditions afforded the desired 5‐n‐octyl‐TPD in a 63 % yield in one step. This is a considerably improved process compared with the most conventional approach (5 steps in 12–22 %) In addition, this method was applied to the syntheses of pyridinopyrroledione (PPD) and pyrroloisoindoletetraone (PIT), which also are important structural components for various functional materials and bioactive compounds. The developed synthetic approach would be a valuable aid to the materials and drug discovery process.

Rhodium-Catalyzed Intramolecular Transannulation Reaction of Alkynyl Thiadiazole Enabled 5,n-Fused Thiophenes

“…First, we commenced our study by optimizing an intramolecular transannulation reaction of alkynyl thiadiazole 1a in the presence of a transition-metal catalyst (Table 1). Rh 2 (oct) 4 (5 mol %) and RhCl 3 •H 2 O (5 mol %)/DPPF (12 mol %) were totally ineffective for the transannulation (entries 2 and 3). However, Rh(PPh) 3 Cl and [Ir(COD)Cl] 2 (5 mol % each) in the presence of DPPF (12 mol %) afforded, gratifyingly, the desired transannulated product 2a in 42% and 16% yields, respectively (entries 1 and 5).…”

“…For this reason, the development of an efficient synthetic method for functionalized fused thiophenes is highly attractive and poses a significant challenge. To date, various synthetic methods of fused thiophenes from easily available compounds have been reported (Scheme a–g): (a) a one-pot, three-step reaction of 3,4-dibromothiophene using n -BuLi, 1-benzylpiperidin-4-one, CO 2 , and Ac 2 O, (b) basic hydrolysis and subsequent ring closure of a dicarboxylic acid after a Rosenmund–von Braun reaction of 3,4-dibromothiophene, (c) a Pd-catalyzed carbonylative amidation of 3,4-dibromothiophene, (d) a condensation reaction of thiophene dicarbaldehydes and aromatic amines in the presence of 2-mercaptoethanol, (e) Friedel–Crafts acylation of thiophene-3,4-dicarbonyl dichloride and benzene, (f) Suzuki–Miyaura cross-coupling of bromoarylcarboxylate and o -hydroxyarylboronic acid, and (g) reaction of o -hydroxyacetophenone with ethyl cyanoacetate and elemental sulfur under microwave conditions . However, because some of the previously reported synthetic methods demand a strong base, long reaction times, and vigorous reaction conditions, the development of efficient synthetic approaches to overcome these shortcomings has been continuously required.…”

Recent advances of Imide-functionalized polymer Donors for Non-fullerene Solar Cells

“…In 2015, Shinichiro Fuse et al reported the synthesis of TPD through a Pd-catalyzed carbonylative amidation reaction from commercially available 3,4-dibromothiophene in a yield of 63 % (Synthetic route 3). [76] It should be noted it is the most straightforward synthetic route to synthesize TPD by one-step reaction. In 2023, Min et al reported a synthetic route of DT-TPD through a two-step reaction in a yield of 31 %.…”

Regiochemically Pure 1,6-Ditriflato-Perylene Diimide: Preparation and Transformation

“…The starting material 1,6,9,10-tetrabromo-perylene monoimide 1 is synthesized from commercially available 3,4,9,10-perylenetetracarboxylic dianhydride ( PTCDA ) by four steps in 37% overall yield according to the literature reported method . Thanks to the relatively higher reactivity in nucleophilic substitution of bromo groups at the bay-region than those at peri positions, compound 2 can be obtained in a yield of 65–70% by heating a solution of compound 1 in N , N -dimethylformamide along with methanol and potassium carbonate at 80 °C for 4 h. , Subsequently, compound 3 can be achieved in a moderate yield by the one-pot palladium-catalyzed domino carbonylative amidation using carbon monoxide as the source of carbonyl in toluene at 100 °C for 10 h . Through the demethylation reaction, compound 4 can be easily obtained in a yield of 56–60% in the liquidated pyridine hydrobromide .…”