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

Abstract

Abstract:The Mizoroki-Heck reaction represents one of the most convenient methods for carbon-carbon double bond formation in the synthesis of small organic molecules, natural products, pharmaceuticals, agrochemicals, and functional materials. Fluorine-containing organic compounds have found wide applications in the research areas of materials and life sciences over the past several decades. The incorporation of fluorine-containing segments into the target molecules by the Mizoroki-Heck reactions is highly attractive, as these reactions efficiently construct carbon-carbon double bonds bearing fluorinated functional groups by simple procedures. This review summarizes the palladium-catalyzed Mizoroki-Heck reactions using various fluorine-containing reagents as the cross-coupling partners. The first part of the review describes the Pd-catalyzed Mizoroki-Heck reactions of aryl halides or pseudo-halides with the fluorinated alkenes, and the second part discusses the Pd-catalyzed Mizoroki-Heck reactions of the fluorinated halides or pseudo-halides with alkenes. Variants of the Pd-catalyzed Mizoroki-Heck reactions with fluorine-containing reagents are also briefly depicted. This work supplies an overview, as well as a guide, to both younger and more established researchers in order to attract more attention and contributions in the realm of Mizoroki-Heck reactions with fluorine-containing participants.

Facile Peptide Bond Formation: Effective Interplay between Isothiazolone Rings and Silanol Groups at Silver/Iron Oxide Nanocomposite Surfaces

“…According to the mechanism of Heck reaction, alkyl iodides and alkyl bromides are preferred for this approach due to having more suitable leaving groups. 28 In this work, it has been shown that alkyl chlorides could also be used in the Heck reactions using partial amounts of silver nitrate as a modifier. Through using AgNO 3 , we could either modify the Heck reaction between 5-chloro-2-methyl-4-isothiazolin-3-one (CMI) and surface vinyl groups to raise the yield of the reaction and also produce Ag/Fe 3 O 4 @SiO 2 -IT nanocomposites as the desired nanoscale product (Scheme 1).…”

Immobilizing palladium on melamine‐functionalized magnetic nanoparticles: An efficient and reusable phosphine‐free catalyst for Mizoroki–Heck reaction

“…Generally, phosphine‐based Pd catalysts such as Pd(PPh 3 ) 4 and PdCl 2 (PPh 3 ) 2 are employed as catalyst for the Heck reaction. [ 8–10 ] However, the main drawbacks with these phosphine–Pd catalyst systems are related to the fact that most of the phosphine derived ligands are toxic, highly expensive and moisture and air sensitive. [ 11 ] To overcome these limitations, enormous efforts have been devoted to synthesize various nonphosphine‐based homogeneous catalytic systems with new types of ligands such as palladacycles, [ 12,13 ] N ‐heterocyclic carbine, [ 14 ] and pincer ligands.…”

Enantioselective construction of remote tertiary carbon–fluorine bonds

“…Thus, alkenyl fluorides have been reported as substrates for Heck-type reactions with insertion occurring at C B but with various caveats. [29][30][31][32][33][34][35] The first is that tri-substituted alkenyl fluorides of type 1 have not been described as substrates in Heck reactions and presumably would be poorly reactive due to the high electronegativity of the F substituent and the congested nature of the alkene. 32 Consistent with this, our lab has reported that alkenes bearing only carbon substituents with smaller groups (e.g., disubstituted vs. trisubstituted alkenes) as well as substrates that are more electron rich (e.g., alkyl vs. aryl) react faster in Heck-type reactions.…”