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.

Highlights

  • The palladium-catalyzed carbon-carbon cross-coupling of an aryl or vinyl halide and an alkene in the presence of a base is referred as the “Mizoroki-Heck reaction” [1,2,3,4,5,6]

  • In 1972, Heck and co-worker proposed a possible mechanism for the reactions of aryl, benzyl, or styryl halides (R–X) with alkenes and a catalytic amount of Pd(OAc)2 under milder conditions (Scheme 1) [9]

  • Bifunctionalization of alkenes triggered by the Mizoroki-Heck reactions has attracted fluoroalkylative cyclization of olefins (227) with RfnI (228), which offered an efficient method for the great attention in organic

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Summary

Introduction

The palladium-catalyzed carbon-carbon cross-coupling of an aryl or vinyl halide and an alkene in the presence of a base is referred as the “Mizoroki-Heck reaction” [1,2,3,4,5,6]. In 1972, Heck and co-worker proposed a possible mechanism for the reactions of aryl, benzyl, or styryl halides (R–X) with alkenes and a catalytic amount of Pd(OAc) under milder conditions (Scheme 1) [9]. There has been no review article systematically summarizing the Pdcatalyzed Mizoroki-Heck reactions using fluorine-containing agents as the cross-coupling partners. Mizoroki-Heck reactions using fluorine-containing agents as the cross-coupling partners.

Fluoroalkenes as Cross-Coupling Participants
Pd-catalyzed
Participants
Heck-Matsuda
10. Theand oxidative
47 AcOH examples including
16. TheThe
F7with
20. The Mizoroki-Heck of CF2 CF2alkenes
24. Synthesis
Fluorinated
F5 bond was retarded addition
33. Pd-catalyzed
34. Synthesis
36. Synthesis of fluorine-containing pyridine C-nucleosides via the
37. Synthesis
RCF22X
40. Palladium-catalyzed Heck-type
42. Palladium-catalyzed
43. Pd-catalyzed
Variants of Bifunctionalization the Mizoroki-Heck
47. Pd-catalyzed
Conclusions
Findings
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