C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions
2011 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 9, no 18, 6246-6255 p.Article in journal (Refereed) Published
The reactivity of bis-TMS-substituted C,C-diacetylenic phosphaalkene (A(2)PA) 1 in Sonogashira-Hagihara cross-coupling reactions has been examined. The selective and successive deprotection of the two silyl groups in 1 is enabled by the steric bulk of the Mes* group which renders the acetylene trans to Mes* more reactive and thereby facilitates selective and consecutive couplings with iodoarenes. In situ transformation of the TMS-protected acetylenes into Cu(I)acetylides is the key step in the synthetic sequence and enables the preparation of the first dimeric A(2)PA linked by a phenylene spacer. cis-trans Isomerization across the P = C bond is triggered by a tertiary amine and exclusively observed in the case of nitrophenyl-substituted A(2)PAs. The introduced aryl groups are integral parts of the entire p-system as evidenced by spectroscopic and electrochemical studies.
Place, publisher, year, edition, pages
2011. Vol. 9, no 18, 6246-6255 p.
IdentifiersURN: urn:nbn:se:uu:diva-158613DOI: 10.1039/c1ob05705gISI: 000294263900011OAI: oai:DiVA.org:uu-158613DiVA: diva2:440074