N-Oxide incorporation into thiazole-containing conjugated materials can have substantial effects on both the electronic and physical properties. A notably strong non-covalent S–O interaction is observed between the N-oxide and neighbouring sulfur.
A combined experimental and computational investigation was conducted to identify a mild and effective Lewis‐acidic activator for TolIF2 in the gem‐difluorination of diazo compounds. Computationally, borosilicate, a common constituent of laboratory glassware, was found to spontaneously activate TolIF2, and an extensive experimental survey confirmed borosilicate as the most effective activator to date. The key to realizing this borosilicate‐activated reaction was the use of high purity TolIF2, which is prepared by a reproducible, multigram‐scale synthesis.
Treatment of diyne substrates with sulfinate salts under the action of copper(II) triflate results in a cascade cyclization reaction. The reaction involves nucleophilic addition of the sulfinate and formation of two new C-C bonds with concomitant cleavage of an aryl C-H bond. The reaction proceeds in good yields with a range of diyne precursors and sulfinate salts. Preliminary mechanistic analysis reveals a rare example of an operative ionic mechanism in contrast to other related cyclizations.
The development of economical synthetic
methods remains an important
step toward the widespread use of conjugated polymers. Most well-established
methods require either prefunctionalization with organometallic reagents
or the use of expensive transition-metal catalysts. We have shown
that 2-hydroxyalkyl- and 2-hydroxyaryl-substituted thiazole N-oxides can proceed through an ipso-arylative
condensation that yields bithiazole-containing conjugated small molecules
and polymers. The use of 2-hydroxyaryl substituents enables access
to a wide scope of thiazole N-oxide substrates and
presents an economical route to the synthesis of bithiazole-based
conjugated polymers with varying physical and electronic properties.
An oxidative ring opening of benzothiazole to an acylamidobenzene sulfonate ester using alcohol solvents and magnesium monoperxoyphthalate hexahydrate has been described. Under the established conditions, the reaction produces synthetically significant yields with a variety of benzothiazole derivatives. A sulfonate ester intermediate suggests that the reaction proceeds via thiazole ring opening followed by thiol oxidation.
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