Copper-Catalyzed Alkene Arylation with Diaryliodonium Salts

Abstract

Alkenes and arenes represent two classes of feedstock compounds whose union has fundamental importance to synthetic organic chemistry. We report a new approach to alkene arylation using diaryliodonium salts and Cu catalysis. Using a range of simple alkenes, we have shown that the product outcomes differ significantly from those commonly obtained by the Heck reaction. We have used these insights to develop a number of new tandem and cascade reactions that transform readily available alkenes into complex arylated products that may have broad applications in chemical synthesis.

Iodine(III)-Mediated Ring Contraction Reactions: Synthesis of Oxygen- and Nitrogen-Substituted Indanes

“…35 The methoxy functionalized ketones 8h and 8b were also transformed into cyclic alkenes 1h and 1b in 93 and 76% yields, respectively (entries 2 and 3). 13,36,37 The benzoyl, tosyl, Fmoc and acetyl protected amino ketones (7c-f) were smoothly converted into desired olefinic substrates (1c-f) in good yields (entries 4-7).…”

“…few crystals) at 130 o C. The crude product was purified by flash column chromatography (20-40% EtOAc in hexane) giving alkene 1h. 36 Yield: 1.702 g (95%); colorless oil. Under inert atmosphere N 2 , NaH (6.24 g, 260 mmol, 60% in mineral oil) was washed with anhydrous hexanes (3 × 20 mL).…”

Diaryliodonium Salts in Organic Syntheses: A Useful Compound Class for Novel Arylation Strategies

“…65 Formation of two alkene isomers was observed (78 and 79) and the selectivity was influenced by the structure of the alkene and the iodonium salt. Preliminary studies showed that a carbocation-type mechanism was operated in these reactions.…”

“…[54][55][56][57][58][59][60][61][62][63][64][65][66][67] Utilizing this concept, several syntheses of diverse heterocyclic skeletons were developed in the last few years in our and other laboratories. The copper catalyzed synthesis of new oxazoline derivatives (89) from propargyl amides (88) and diaryliodonium salts was recently developed by our research group.…”

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

“…The Mizoroki-Heck reactions are originally catalyzed by palladium [1][2][3][4][5][6]. Other transition metals, such as nickel, cobalt, copper, gold, and iron, are also active catalysts for Heck-type reactions [26][27][28][29][30][31][32][33]. The visible light-induced Pd-catalyzed Mizoroki-Heck reactions between sterically hindered alkyl halides and vinyl arenes have been accomplished, as well [34,35].…”