Oxidative Bond Formation in Dithienyl Polyphenylenes: Optical and Electrochemical Consequences

We describe the synthesis and reactivity of a new class of diazidated compounds: the 2,2‐diazido‐1,2‐diarylethanones. The diazides are easily accessible from 1,2‐diarylethanones through a mild and simple protocol for the direct oxidative diazidation, using iodine and sodium azide in DMSO at room temperature. In studies towards their reactivity with amine nucleophiles under basic conditions, the diazides are shown to undergo a controlled fragmentation reaction that provides a straightforward access to the corresponding amides. In stark contrast to our previous results on the amine‐triggered fragmentation of diazidated compounds, aromatic nitriles are found to be by‐products of synthetic value. The net reaction consisting of diazidation and subsequent fragmentation, thus, provides a simple way to convert 1,2‐diarylethanones into both aromatic amides and nitriles.

show abstract

“…13 C NMR (101 MHz, CDCl 3 ): δ = 129.9, 128.6, 125.5, 122.4, 84.2 ppm. The analytical data are in agreement with previously reported ones …”

Section: Methodssupporting

confidence: 92%

2,2‐Diazido‐1,2‐diarylethanones: Synthesis and Reactivity with Primary Amines

2019

View full text Add to dashboard Cite

show abstract

“…As mentioned, it is known that the β‐positions of thiophenes can be addressed in oxidative coupling reactions even in the presence of free α‐positions, and there are also examples reported for the formation of such α,β′‐connections as a result of geometric reasons . However, in our case, no six‐membered cycle is formed.…”

Section: Resultsmentioning

confidence: 46%

Fast Oxidative Cyclooligomerization towards Low‐ and High‐Symmetry Thiophene Macrocycles

Maier

Poluektov

Jester

et al. 2015

Chemistry A European J

View full text Add to dashboard Cite

Macrocycles with quaterthiophene subunits were obtained by cyclooligomerization by direct oxidative coupling of unsubstituted dithiophene moieties. The rings were closed with high selectivity by an α,β'-connection of the thiophenes as proven by NMR spectroscopy. The reaction of the precursor with terthiophene moieties yielded the symmetric α,α'-linked macrocycle in low yield together with various differently connected isomers. Blocking of the β-position of the half-rings yielded selectively the α,α'-linked macrocycle. Selected cyclothiophenes were investigated by scanning tunneling microscopy, which displayed the formation of highly ordered 2D crystalline monolayers.

show abstract

“…However, there is lack of reports about the influence of this type of interactions on PL, mainly due to synthetic difficulties in 2D-p-conjugated derivatives obtaining. So far, multi-substituted benzene or naphthalene derivatives containing thiophenyls were prepared by: Stille coupling reactions [20,21] Diels-Alder reaction (with CO-extrusion) [22,23], cycloaddition cyclobutene-1,2-diones [24], cyclotrimerization [25] or via intermolecular [2+2+2] cycloaddition catalyzed by Ru(II)-complexes [26]. Recently, in the literature new synthetic route was reported i.e.…”

Section: Introductionmentioning

confidence: 99%

“…What is in the great importance, a wide range of commercially available b-keto esters, as well as the ease in further modification of this building blocks make this strategy very interesting. In the case of Diels-Alder reactions (with CO-extrusion) difficult to obtained cyclopentadienone systems [22], and high temperatures (from 250°C to 300°C) during [4+2] cycloaddition [22,23] are required. On the other hand, similar cycloaddition using 2-pyranon as substrate (i.e.…”

Section: Introductionmentioning

confidence: 99%