A Robust First-Pass Protocol for the Heck–Mizoroki Reaction

Abstract

Supporting informationNMR data (E)-3-p-Tolylacrylic acid methyl ester 17a..

The Application of Advanced Design of Experiments for the Efficient Development of Chemical Processes

“…It is known that the use of non-obvious solvents, such as nonpolar solvents for electron rich Heck reactions, can completely change reaction selectivity [19]. The power of combining PCA and DoE will increase the possibilities for organic and process chemists and is demonstrated in the following Case Studies.…”

The Mizoroki‐Heck Reaction with Internal Olefins: Reactivities and Stereoselectivities

“…Fu's conditions (Scheme ) enabled the Mizoroki‐Heck reaction of internal olefins and simple Ar−Br at room temperature in the presence of P( t ‐Bu) 3 as a ligand for a Pd catalyst. When the Mizoroki‐Heck reaction of internal olefin 8.1 and Ar−Br possessing a heterocycle or a phenol moiety was carried out under similar conditions in the presence of a Pd catalyst [Pd(tBu 3 P) 2 or PdCl 2 (DtBPF) (DtBPF=1,1’‐bis(ditertbutylphosphino)ferrocene)] at 80 °C, products 8.2 are obtained in moderate yields due to catalyst poisoning, but selectivities are perfect (Scheme ) . The Mizoroki‐Heck reaction of internal olefin 9.1 and electron‐deficient Ar−Cl under Pd/DavePhos conditions also results in a moderate yield of 9.2 (Scheme ) .…”

“…When the Mizoroki-Heck reaction of internal olefin 8.1 and ArÀ Br possessing a heterocycle or a phenol moiety was carried out under similar conditions in the presence of a Pd catalyst [Pd (tBu 3 P) 2 or PdCl 2 (DtBPF) (DtBPF = 1,1'-bis(ditertbutylphosphino) ferrocene)] at 80°C, products 8.2 are obtained in moderate yields due to catalyst poisoning, but selectivities are perfect (Scheme 8). [13] The Mizoroki-Heck reaction of internal olefin 9.1 and electron-deficient ArÀ Cl under Pd/DavePhos conditions also results in a moderate yield of 9.2 (Scheme 9). [14] These results clearly illustrate the low reactivity of internal olefins for the Mizoroki-Heck reaction.…”

Synthesis of meso-tetra-(5-iodo-thien-2-yl)-porphyrin; an intermediate for cross-coupling reactions

“…One way to functionalize these compounds is the Heck-Mizoroki and Sonogashira cross coupling reactions. 4 We now propose the synthesis of meso-thien-2-yl-porphyrins functionalized with iodine, ready for cross-coupling reactions.…”