Recent Advances of Catalytic Enantioselective Heck Reactions and Reductive‐Heck Reactions

Abstract

Heck reaction is one of the most important carbon‐carbon bond forming reactions with wide applications in organic synthesis. Considerable advances of enantioselective Heck reaction have been achieved in the past decades. This review focuses on recent development of catalytic asymmetric Heck reaction and reductive Heck reaction, which covers intermolecular and intramolecular versions since 2011. The article is organized in terms of the catalysts and olefin substrates.

In Tandem Auto‐Sustainable Enantioselective Heck‐Matsuda Reactions Directly from Anilines

“…The enantioselective palladium‐catalyzed Heck reaction is a reliable synthetic method to construct new C−C bonds and stereogenic centers in the synthesis of complex molecules [1,2] . In particular, the Heck arylations using aryl (pseudo)halides play an important role in the synthesis of natural products and complex biologically active compounds [3–6] .…”

“…The enantioselective palladium-catalyzed Heck reaction is a reliable synthetic method to construct new CÀ C bonds and stereogenic centers in the synthesis of complex molecules. [1,2] In particular, the Heck arylations using aryl (pseudo)halides play an important role in the synthesis of natural products and complex biologically active compounds. [3][4][5][6] Although lesser developed, the Heck arylations employing arenediazonium salts -the Heck-Matsuda (HM) reactionsincorporate several advantages when compared to Heck arylations employing aryl (pseudo)halides, such as higher reactivity, operational simplicity, open-flask handling, milder, and greener reaction conditions.…”

Palladium-Catalyzed Cascade Dearomative Spirocyclization and C−H Annulation of Aromatic Halides with Alkynes

“…Although this work obviated the using of electronically activated aromatics as starting materials, an alkyl group is necessary to enable a β-hydrogen elimination as the driving force for the expected spirocyclization reaction (Scheme a). Recently, the endocyclic C=C bonds of (hetero)­arenes have been regarded as nonclassic olefins to enable the dearomative difunctionalization reactions . In this regard, Jia and You reported the catalytic dearomative 1,4-difunctionalization of naphthalenes by capturing the in situ formed π-allyl-palladium species with a second coupling partner (Scheme b). , Inspired by this dearomative difunctionalization strategy, we envisioned that the catalytic Heck-type dearomative spiroannulation of polycyclic aromatic halides with diaryl acetylenes could be achieved without the assistance of an alkyl group, by intercepting the alkyl palladium intermediates with the attached aryl rings on the carbon–carbon triple bonds.…”

Nickel-Catalyzed Reductive Asymmetric Aryl-Acylation and Aryl-Carbamoylation of Unactivated Alkenes

“…In the last decade, transition-metal catalyzed enantioselective dicarbofunctionalizations of tethered alkenes has evolved into a reliable method to construct the scaffold of chiral benzene-fused cyclic compounds. [1][2][3][4][5][6] The majority of these reactions relies on a facially selective Heck-type arylmetallation of the pendant olefinic unit as the enantiodetermining step, 7 which is followed by trapping of the generated σ-alkylmetal species with either a nucleophile or an electrophile. Based on this strategy, asymmetric aryl-alkylation, [8][9][10] diarylation, [10][11][12][13] arylbenzylation, 14 aryl-alkenylation 15,16 and aryl-alkynylation 13,17,18 of incorporated alkenes have been developed under palladium, copper or nickel catalysis.…”