1‐Phospha‐Butadienes and 1H‐Phospholes via Alkynylation of Acetylenic Phosphaalkenes. Issue 4 (3rd April 2023)

• Record Type: Journal Article
• Authors: Anwar Shameem, Muhammad; Kumar Gupta, Arvind; Erdelyi, Mate; Orthaber, Andreas
• Is Part Of: ChemPlusChem. Volume 88:Issue 4(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-04-03
• Subjects: acetylenic phosphaalkenes -- alkynylation -- phosphole -- π-conjugation -- Sonogashira coupling; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.202300054
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: Carbon‐rich motifs are important building blocks for the fabrication of functional and opto‐electronic materials. Electronic tuning can be achieved by alteration of bonding topologies but also via incorporation of heteroelements, for example phosphorus. Herein we present the palladium/copper mediated formation of branched 1‐phospha‐butadiene derivatives through an unusual alkynylation of a phospha‐enyne fragment. Structural and NMR studies provide mechanistic insights into this alkynylation. Furthermore, we disclose a complex cyclisation of the thus obtained 3‐yne‐1‐phosphabutadiene motifs to give highly substituted phosphole derivatives identified by 2D NMR and SC‐XRD analysis. Abstract : Reactions of acetylenic phosphaalkenes are reported in this work, i. e. a concerted palladium and copper mediated formation of branched 1‐phospha‐butadiene derivatives through an unusual alkynylation of a 1‐phospha‐enyne fragment, followed by a complex cyclisation of the 3‐yne‐1‐phosphabutadiene motifs; this sequence gives access to highly substituted phosphole derivatives.