A Calixarene‐Decorated Phosphole Oxide. Issue 18 (13th June 2016)

• Record Type: Journal Article
• Authors: Elaieb, Fethi; Hedhli, Ahmed; Sémeril, David; Matt, Dominique; Harrowfield, Jack
• Is Part Of: European journal of organic chemistry. Issue 18(2016)
• Page Start: 3103
• Page End: 3108
• Publication Date: 2016-06-13
• Subjects: Calixarenes -- Phosphanes -- Alkynes -- Phosphole -- Palladium -- Copper; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201600381
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : A conical calix[4]arene receptor equipped with a benzo[ b ]phosphole oxide grafted to its upper rim was obtained in six steps by starting from 5‐bromo‐25, 26, 27, 28‐tetrapropyloxycalix[4]arene. The route involved the synthesis of the calixarene intermediate5 that bears a 2‐(diphenylphosphinyl)phenylethynyl substituent connected to the calixarene wider rim. Under Pd II /Cu I co‐catalysis, mixed phosphane‐alkyne5, when heated at 120 °C, underwent P–Ph bond cleavage followed by attack of the phosphorus atom onto the carbon–carbon triple bond. The resulting calixarene‐phosphole was then oxidised to form the corresponding phosphole oxide9 . Compound9 luminesces strongly under UV irradiation. The solid‐state structure of a derivative of phosphane‐alkyne5, AuCl complex8, was established by a single‐crystal X‐ray diffraction study. Abstract : A convenient method is described to graft a calixarenyl receptor unit onto a phosphole ring, to give a stable phosphole oxide product that exhibits strong luminescence. This methodology requires preparation of a 2‐(phenylethynyl)phosphane intermediate.