Trifunctionalization of aryl iodides via intermolecular C–H acylation/intramolecular C–H alkylation achieved using palladium/norbornene cooperative catalysis

Abstract

Herein we describe a palladium/norbornene catalyzed trifunctionalization of ortho-unsubstituted aryl iodides via a highly chemoselective cascade process involving intermolecular ortho acylation/intramolecular ortho alkylation/ipso alkenylation. This approach provides a modular and...

Modular Synthesis of ortho‐Thiolated Aryl Esters Enabled with Thiocarbonate through Catellani Strategy

“…The crux for the success of this transformation is formation of aryl‐NBE palladacycle (ANP) intermediate from aryl halides, norbornene, and palladium [10] . Pioneering contributions from the groups of Catellani, [11] Lautens, [13a] Dong, [12b] Zhou, [15c] and others [12a,19b,22] have shown various of terminating reagents, such as alkene, [12] organometallic reagents, [13] heteroatom, [14] and so on, [15] can be coupled with ipso‐ carbon via classical cross‐coupling reactions. It is worth mentioning that compared with ortho ‐position alkylation, [16] arylation, [17] amination, [18] and acylation, [19] which have received much attention, ortho ‐thiolation [20] and ortho ‐alkoxycarbonylation [21] have only been reported in a few cases.…”