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

Abstract

The Mizoroki‐Heck reaction is one of the most valuable reactions for functionalizing C−C double bonds in the presence of a Pd catalyst. This protocol is suitable for the reaction of a C(sp2)‐halide with a terminal olefin to produce a trans‐1,2‐disubstituted olefin. However, reports of the Mizoroki‐Heck reaction of internal olefins are rare and impractical due to the low reactivity of internal olefins and problems of product diastereoselectivity. In this review, we summarize Mizoroki‐Heck reactions of internal olefins with aryl or alkyl halides to illustrate their reactivities and stereoselectivities.

2‐Pyridyl‐Benzimidazole‐Pd (II) Complex Supported on Magnetic SBA‐15: An Efficient and Magnetically Retrievable Catalyst for the Heck Reaction

“…Among the various transition‐metal‐catalyzed reactions for making C−C bond, the Mizoroki‐Heck reaction is one of the most powerful methods. The reaction was independently discovered by Mizoroki and Heck, and they were awarded in 2010 the Nobel prize in chemistry with Suzuki and Negishi [1] . During the Mizoroki‐Heck reaction, functionalized alkenes are obtained via coupling of aryl (pseudo)halides and alkenes.…”

“…The reaction was independently discovered by Mizoroki and Heck, and they were awarded in 2010 the Nobel prize in chemistry with Suzuki and Negishi. [1] During the Mizoroki-Heck reaction, functionalized alkenes are obtained via coupling of aryl (pseudo)halides and alkenes. The reaction has found a special place in laboratory as well as in industry due to serving transition metals in a smooth manner during the catalytic cycle.…”

Visible-Light Photoredox Catalyzed Dehydrogenative Synthesis of Allylic Carboxylates from Styrenes

“…Unactivated olefins are convenient feedstocks in organic synthesis due to their large availability and intrinsic wide chemical flexibility. 1 Generally, the chemical manipulation of alkenes requires site-selective electrophilic activation of the π-system using noble transition metals or harsh Brønsted acidic conditions. Very recently, radical variants started flanking these approaches 2 with the use of dedicated visible-light induced generation of radical cations that could evolve into chemical diversity/complexity via subsequent stoichiometric oxidant-free dehydrogenative couplings.…”

“…Unactivated olefins are convenient feedstocks in organic synthesis due to their large availability and intrinsic wide chemical flexibility . Generally, the chemical manipulation of alkenes requires site-selective electrophilic activation of the π-system using noble transition metals or harsh Brønsted acidic conditions.…”

Pd‐Catalyzed Regioselective Olefination of N‐Tosylhydrazones with Benzyl Bromides

“…[1][2][3] Therefore, the skeleton construction of olefins had become an important research area in organic synthesis. At present, the preparation methods of commonly substituted olefins mainly included transition metal-catalyzed Mizoroki-Heck reaction, [4] Wittig reaction, [5] and other related synthetic routes. [6][7][8][9] However, these methods usually involved one of the following deficiencies, such as harsh reaction conditions, the use of air-sensitive organometallic reagents or complex substrate precursors, and higher reaction temperature.…”