Intermolecular Mizoroki–Heck Reaction of Aliphatic Olefins with High Selectivity for Substitution at the Internal Position

Abstract

Neuer Ligand für alte Reaktion: Die Titelreaktion von Aryltriflaten mit aliphatischen Olefinen führt mit hoher Selektivität zur Substitution an der internen Position. Das Verhältnis des gewünschten Isomers (siehe Schema) zur Summe der anderen Isomere ist größer als 10:1. Entscheidend ist der verwendete Ferrocen‐Bisphosphan‐Ligand (R=1‐Naphthyl). Der Reaktionsmaßstab kann vergrößert werden, und die ungewünschten Isomere können chromatographisch abgetrennt werden.

General Olefin Synthesis by the Palladium‐Catalyzed Heck Reaction of Amides: Sterically Controlled Chemoselective NC Activation

“…Styrenes and electron deficient olefins provide the products in high yields and with excellent regioselectivity. [23] Acrylic esters (entries 2a nd 3), amides (entry 4) and nitriles (entry 5) are well-tolerated. [23a] Te rminal olefins can be used as substrates (entry 6); [23b] however,o lefin isomerization results in am ixture of isomers,i na greement with previous studies.…”

General Olefin Synthesis by the Palladium‐Catalyzed Heck Reaction of Amides: Sterically Controlled Chemoselective NC Activation

“…The chemoselective coupling of amides nicely illustrates the synthetic potential of the amide bond activation platform via distortion. [23] Acrylic esters (entries 2a nd 3), amides (entry 4) and nitriles (entry 5) are well-tolerated. Thes cope of olefin coupling partners is also very broad (Table 3).…”

Nickel‐Catalyzed Mizoroki–Heck Reaction of Aryl Sulfonates and Chlorides with Electronically Unbiased Terminal Olefins: High Selectivity for Branched Products

“…[10] In the past year, this field has seen renewed interest. Zhou and coworkers reported the Pd-catalyzed Heck reaction of terminal olefins [11] and vinylarenes [12] with aryl triflates in good yields. Stahl and coworkers also reported the oxidative Heck reaction of vinyl boronic acids and terminal olefins using Pd and a phenanthroline-type ligand.…”