Various substituted dioxythiophenes bearing 3,4-propylenedioxythiophenes (ProDOT) and 3,4-ethylenedioxythiophene (EDOT) moieties successfully undergo Pd-catalyzed direct C−H arylation to yield π-conjugated polymers. The effects of palladium catalysts, phosphine ligands or additives, and functional groups on this facile polycondensation approach are investigated. Polymers from alkoxy-substituted ProDOT are synthesized with reasonable molecular weight (M n = 6100−9600) and low PDI (1.3−1.9). Four substituted EDOT with alkoxy or protected functional groups also undergo direct C−H arylation polycondensation to yield corresponding polymers. The obtained polydioxythiophenes exhibit UV−vis absorptions ranging from 480 to 590 nm, and these conjugated polymers are electroactive and reversibly switched between the oxidized and neutral states upon applying potentials.
[reaction: see text] The reaction of iodo- or bromo-substituted aryltriazenes with i-PrMgCl.LiCl generates the corresponding magnesiated derivatives which react with various electrophiles (acid chlorides, 3-iodoenones, allylic halides, aldehydes) affording polyfunctional triazenes. They can be readily converted to the corresponding polyfunctional aryl iodides. This new synthetic strategy was applied to prepare functionalized carbazoles.
A wide range of directing groups (ester, ketone, acetate, aryl sulfonate, triazene, carbamate) allow the regioselective directed ortho insertion (DoI) of zinc in the presence of LiCl leading to polyfunctional aryl and heteroaryl zinc reagents.
CuCN reacts with RLi and TMPLi (TMP3 and 3•LiCN haVe been tested in directed ortho cupration with data suggesting enhanced efficiency for Lipshutz-type 3•LiCN; competition between Lipshutz-and Gilman-type formulations is rationalized by DFT methods.
A variety of 3,4-ethylenedioxythiophene (EDOT)-based π-conjugated molecules were efficiently synthesized in good yields through Pd-catalyzed direct C-H bond arylations, wherein a detailed synthetic investigation, including the screening of various kinds of palladium catalysts, ligands, additives, and solvents, was carried out. In addition, the spectroscopic and electrochemical properties of these EDOT-containing molecules were also investigated.
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