Facile access to sterically hindered aryl ketones via carbonylative cross-coupling: application to the total synthesis of luteolin

• Published in: Tetrahedron Vol. 67; no. 24; pp. 4344 - 4351
• Main Authors: O’Keefe, B. Michael, Simmons, Nicholas, Martin, Stephen F.
• Format: Journal Article
• Language: English
• Published: England Elsevier Ltd 17-06-2011
• Subjects: Aromatic compounds; Arrays; Aryl ketones; Carbon monoxide; Carbonyls; Catalysts; Cross coupling; Ketones; N-Heterocyclic carbene; Natural products; Palladium; Phosphines; Synthesis (chemistry); Total synthesis; Aryl ketones; Cross-coupling; Natural products; N-Heterocyclic carbene; Palladium; Carbon monoxide; Total synthesis
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2011.03.074

A general and mild protocol for achieving the carbonylative cross-coupling of sterically hindered,
ortho-disubstituted aryl ketones is reported. The commercially available PEPPSI-IPr catalyst is shown to efficiently promote the carbonylative cross-coupling of hindered
ortho-disubstituted aryl iodides to give diaryl ketones; traditional phosphine catalysts are less effective. Carbonylative Suzuki-Miyaura cross-couplings provide a diverse array of biaryl ketones in good to excellent yields. The same catalyst is also shown to catalyze a carbonylative Negishi cross-coupling reaction, utilizing a variety of alkynyl-zinc reagents to give the corresponding alkynyl aryl ketones. Application of this new methodology to the synthesis of the natural product luteolin is reported.
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