Scalable Synthesis of Naphthothiophene-based D-π-D Extended Oligomers through Cascade Direct Arylation Processes

Abstract

The synthesis of two novel π-extended oligomers, incorporating naphtho[1,2-b]thiophene-4-carboxylate 2-octyldodecyl esters as end-capping moieties, and two different conjugated core fragments, has been achieved through a cascade sequence of sustainable organic reactions. Benzo[c][1,2,5]thiadiazole and 2-octyldodecyl benzo[1,2-b:6,5-b′]dithiophene-4-carboxylate have been used, respectively, as electron-poor and electro-rich π-conjugated cores. In the latter case, a sequence of nine aromatic rings in a fully conjugated structure is achieved with a high yielding, sustainable cascade approach. The optoelectronic properties of both oligomers are reported.

Anthradithiophene (ADT)‐Based Polymerized Non‐Fullerene Acceptors for All‐Polymer Solar Cells

“…Synthetic schemes for P1-P3 are reported in Figure 3a with characterization data provided in Table 1. Monomer 2 can be straightforwardly synthesized in high yield following the procedure reported previously, [47,49] from inexpensive and readily available starting materials through an innovative cascade of direct arylation/cross-aldolization reactions [46,[49][50][51][52] while NFA building blocks are commercially available. Polymers P1-P3 were synthesized by Stille coupling polycondensation reactions…”

Aminothiaindanone as an Accessible Scaffold for a Three-Point Chemical Diversity

“…Moreover, synthetic access to this scaffold remains relevant as can be seen from recent works in carbonylation, 26 in carbocyclization, [27][28][29] direct functionalization 30,31 or in annulation of thiophene heterocycles. [32][33][34][35] Therefore, the present study has been done to explore the possible functionalization of aminothiaindanone scaffold with three diversity points: first on the thiophene ring, second on the amine group, and finally third on the ketone part of the scaffold.…”

“…The synthetic pathway was adapted from earlier work of our laboratory using different reagents to optimize the protocols. 33,34 3-Amino-3-(2-thienyl)propanoic acid 4 was synthesized from commercial thiophene-3-carboxaldehyde using the Rodionow-Johnson reaction, which allows to obtain directly β-amino acids from the aldehydes by reaction with malonic acid and ammonia. The β-amino acid 4 was isolated in modest yield (30%) due to the formation of known by-products, i.e.…”

Solution-processable thin-film transistors from anthradithiophene (ADT) and naphthothiopene (NT) small molecule-based p-type organic semiconductors

“…The multi-gram scale synthetic approach makes good use of a cascade annulative protocol, performed by combining a sequence of three reactions: intermolecular direct heteroarylation (DHA), [28][29][30][31] intramolecular cross-aldol condensation and, at last, alkylation of the carboxylic acid functionalities installed onto the p-core, to introduce flexible, alkyl chain to improve solubility and processability. [32][33][34][35][36][37][38] The ester substituents have a key role, as electron-withdrawing substituents adjacent to an enolizable methylene group, for our key annulation reaction, since they activate the cross-aldol condensation. In our synthetic design the carboxylic acid functionalities can be viewed as ''chemical handles'' for the introduction of solubilizing alkyl side chains, although they represent a perturbation of the overall electron donating character of the ADT core.…”