Synthese des 5,6-Didehydro-11,12-dihydro-dibenzo-[a,e]cyclooctens - eines hochgespannten Cycloalkyns

Click Functionalization of a Dibenzocyclooctyne‐Containing Conjugated Polyimine

“…[35][36][37] This led us to explore polymerization methods that do not involve the use of transition-metal catalysts,i ncluding reactions such as the Wittig,H orner-Wadsworth-Emmons, [38][39][40] Aza-Wittig, [41,42] and Knoevenagel condensation, [43] as well as Schiff-base formation. [50][51][52][53][54] In our hands,t he synthetic approach based on aWittig-PrØvost homologation sequence was found to be compatible with initial introduction of aryl halides (in this case,i odides), which could subsequently be converted into the required amines in the target monomer 6 (DIBO-(NH 2 ) 2 ). Amongst these,S chiff-base formation offers several advantages:i thas been well-explored, [46][47][48] can produce high-molecular-weight polymers,a nd the installation of amine groups is straightforward to achieve by using Buchwald-Hartwig chemistry.…”

“…[49] Thestructurally most simple parent structure,dibenzocyclooctyne (DIBO), [50] is ideal as am onomer for conjugated polymer synthesis because it has ar elatively planar, symmetrical structure. [50][51][52][53][54] In our hands,t he synthetic approach based on aWittig-PrØvost homologation sequence was found to be compatible with initial introduction of aryl halides (in this case,i odides), which could subsequently be converted into the required amines in the target monomer 6 (DIBO-(NH 2 ) 2 ). As illustrated in Scheme 1, starting with dibenzosuberone,s tandard iodination conditions generated diiodosuberone 1 in modest yield.…”

Click Functionalization of a Dibenzocyclooctyne‐Containing Conjugated Polyimine

“…The structurally most simple parent structure, dibenzocyclooctyne (DIBO), is ideal as a monomer for conjugated polymer synthesis because it has a relatively planar, symmetrical structure . In our hands, the synthetic approach based on a Wittig–Prévost homologation sequence was found to be compatible with initial introduction of aryl halides (in this case, iodides), which could subsequently be converted into the required amines in the target monomer 6 (DIBO‐(NH 2 ) 2 ).…”

Study and application of noncatalyzed photoinduced conjugation of azides and cycloocta-1,2,3-selenadiazoles

“…A cyclooctyne system can also be generated from a corresponding 1,2,3-selenadiazole, which is easily prepared by converting cyclooctanone to its semicarbazone, followed by its subsequent reaction with selenium dioxide. [14][15][16] However, the transformation of cycloocta-1,2,3-selenadiazole derivatives into cyclooctynes requires harsh conditions, such as thermolysis at temperatures over 115 1C, [17][18][19] thermolysis on copper powder, [20][21][22][23][24] or a reaction mediated by n-BuLi. 14 Such conditions limit the direct use of cycloocta-1,2,3-selenadiazoles for the labeling of biomolecules and the isolation of a generated cyclooctyne system must precede the azide-cyclooctyne conjugation.…”