Rhodium(III)-Catalyzed C–H Olefination for the Synthesis of ortho-Alkenyl Phenols Using an Oxidizing Directing Group

Abstract

By using an oxidizing directing group, a mild, efficient Rh(III) catalyzed C-H olefination reaction between N-phenoxyacetamides and alkenes was developed. This reaction provided a straightforward way for the synthesis of ortho-alkenyl phenols, and the directing group is traceless in the product.

Transition Metal‐Catalyzed Directing‐Group‐Assisted C−H Activation of Phenols

“…The acetamido group was also found to be able to direct Rh‐catalyzed ortho ‐C−H alkenylation of phenols with olefins by Lu, Liu, and co‐workers (Scheme ) . In this procedure, the C−H activation was always inclined to take place at the less hindered position of the phenol rings.…”

Comparison of the Reactivities and Selectivities of Group 9 [Cp*MIII] Catalysts in C−H Functionalization Reactions

“…[24] Under their optimized rhodium-catalyzed conditions, various olefins, including acrylate, acrylonitrile, vinylphosphonate, and styrene derivatives, reacteds moothly,t hereby affording the corresponding alkenylated products. In 2013, Liu, Lu, andc o-workersr eported as ynthesis of ortho-alkenyl phenols that proceeded through a[ Cp*Rh III ]-catalyzed CÀHo lefination pathway (Scheme 15 a).…”

Synthese nichtnatürlicher Aminosäuren durch die regioselektive Cobalt(III)‐katalysierte intermolekulare Carboaminierung von Alkenen

“…[10a] In diesem Bericht konnte die b-Hydrid-Eliminierung durch eine koordinative Absättigung des entstehenden C(sp 3 )-Rhodium-Intermediats durch eine in situ generierte zweizähnige dirigierende Gruppe unterdrückt werden (Schema 1a). [11] Dies geht einher mit signifikanten Limitierungen im Reaktionsanwendungsbereich,s odass weitere Ligandenmodifikationen sowie mehrstufige Substratsynthesen erforderlich sind. [10b] Beiden Berichten gemeinsam ist, dass eine koordinative Absättigung des Metallzentrums füreine erfolgreiche Carboaminierung essentiell notwendig ist.…”