170160-98-2Relevant articles and documents
Strain-Promoted Double Azide Addition to Octadehydrodibenzo[12]annulene Derivatives
Fukushima, Satomi,Ashizawa, Minoru,Kawauchi, Susumu,Michinobu, Tsuyoshi
, (2019)
Octadehydrodibenzo[12]annulenes (DBAs), readily available by the oxidative acetylenic coupling of 1,2-diethynylbenzene derivatives, were reacted with organic azides. As compared to the well-known strain-promoted azide-alkyne cycloaddition (SpAAC) of 5,6,11,12-tetradehydrodibenzo[a,e][8]annulene, the reactivity of the DBA alkynes was lower due to the lower strain energy. However, the regioselective double azide addition occurred without any side reactions under mild conditions, yielding bis-triazole products. The structures of the products were confirmed by an X-ray crystal structure analysis, and the reaction mechanism was studied by 1H-NMR spectroscopy and computational studies. It was also found that the DBAs were hardly fluorescent, while the bis-triazole products showed a green fluorescence with quantum yields up to 5.1 %. Finally, the new strain-promoted double azide addition to the DBAs was used for step-growth polymerization, successfully producing a high molecular weight triazole polymer.
CO extrusion in homogeneous gold catalysis: Reactivity of gold acyl species generated through water addition to gold vinylidenes
Bucher, Janina,St?sser, Tim,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
, p. 1666 - 1670 (2015/01/30)
Herein, we describe a new gold-catalyzed decarbonylative indene synthesis. Synergistic σ,π-activation of diyne substrates leads to gold vinylidene intermediates, which upon addition of water are transformed into gold acyl species, a type of organogold compound hitherto only scarcely reported. The latter are shown to undergo extrusion of CO, an elementary step completely unknown for homogeneous gold catalysis. By tuning the electronic and steric properties of the starting diyne systems, this new reactivity could be exploited for the synthesis of indene derivatives in high yields.
Grignard reagent/CuI/LiCl-mediated stereoselective cascade addition/cyclization of diynes: A novel pathway for the construction of 1-methyleneindene derivatives
Li, De-Yao,Wei, Yin,Shi, Min
supporting information, p. 15682 - 15688 (2013/11/19)
Diynes containing a cyclopropane group smoothly undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1-methyleneindene derivatives in moderate to good yields. This interesting transformation is mediated by Grignard reagent/CuI with LiCl as an additive under mild conditions. The obtained product can easily be further functionalized through cyclopropyl ring opening. A plausible reaction mechanism has also been presented on the basis of deuterium labeling and control experiments. Diyne cyclization: Diynes containing a cyclopropane group undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1-methyleneindene derivatives (see scheme). The transformation proceeds under mild conditions and is promoted by a combination of Grignard reagent Copyright
