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Zhen-Yao Dai

Bio: Zhen-Yao Dai is an academic researcher from University of Science and Technology of China. The author has contributed to research in topics: Allylic rearrangement & Alkylation. The author has an hindex of 3, co-authored 4 publications receiving 76 citations.

Papers
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Journal ArticleDOI
TL;DR: Experimental and computational studies on the reaction mechanism suggest a novel concerted proton and two-electron transfer process for the allylic C-H cleavage and reveal that the Z/ E- and regioselectivities are governed by the geometry and coordination pattern of nucleophiles.
Abstract: The asymmetric allylic alkylation (AAA), which features employing active allylic substrates, has historical significance in organic synthesis. The allylic C–H alkylation is principally more atom- a...

77 citations

Journal ArticleDOI
TL;DR: A palladium-catalyzed asymmetric α-allylation of aldehydes with alkynes has been established by integrating the catalysis of enamine and chiral hydridopalladium complex that is reversibly formed from the oxidative addition of Pd(0) to chiral phosphoric acid.

35 citations

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TL;DR: In this article, an asymmetric photocatalytic C(sp3)-H bond addition to α-substituted acrylates by using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst and chiral phosphoric acid as a chiral proton-transfer shuttle is described.

30 citations

Journal ArticleDOI
TL;DR: Asymmetric allylic C-H alkylation of 1,4-pentadienes with α-angelica lactones has been developed by tri-axial phosphoramidite-palladium catalysis as mentioned in this paper.

14 citations


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Journal ArticleDOI
TL;DR: A comprehensive review of the synthetic applications of photocatalyzed d-HAT can be found in this article, where the authors provide a comprehensive overview of the main applications of PCHAT.
Abstract: Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration of aliphatic C-H bonds. In this manifold, a photocatalyst (PCHAT) exploits the energy of a photon to trigger the homolytic cleavage of such bonds in organic compounds. Selective C-H bond elaboration may be achieved by a judicious choice of the hydrogen abstractor (key parameters are the electronic character and the molecular structure), as well as reaction additives. Different are the classes of PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, a metal-oxo porphyrin and a tris(amino)cyclopropenium radical dication. The processes (mainly C-C bond formation) are in most cases carried out under mild conditions with the help of visible light. The aim of this review is to offer a comprehensive survey of the synthetic applications of photocatalyzed d-HAT.

261 citations

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TL;DR: In this paper, a transition metal complex serves a double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via a single catalytic cycle, thus contrasting the established dual photocatalysis in which an exogenous photosensitizer is employed.
Abstract: In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which has led to the discovery of unprecedented transformations as well as the improvement of known reactions. In this subfield of photocatalysis, a transition metal complex serves a double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via a single catalytic cycle, thus contrasting the established dual photocatalysis in which an exogenous photosensitizer is employed. In addition, this approach often synergistically combines catalyst-substrate interaction with photoinduced process, a feature that is uncommon in conventional photoredox chemistry. This Review describes the early development and recent advances of this emerging field.

198 citations

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TL;DR: In this article, the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions are discussed.
Abstract: This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

175 citations

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TL;DR: An overview of hydrofunctionalisation and difunctionalisation of dienes, allenes, and alkynes is provided, and the chiral ligand used in this area of research is summarized.
Abstract: Hydrofunctionalisation and difunctionalisation of dienes, allenes, and alkynes are widely utilized in the synthesis of valuable allylic compounds. In the past decades, asymmetric catalysis has emerged as one of the most attractive fields in organic synthesis. Recently, the asymmetric versions of hydrofunctionalisation and difunctionalisation reactions have become powerful and compelling tools to afford enantiopure allylic compounds, appealing to a large range of chemists. Various metal complexes modified with a large number of chiral ligands and several chiral organocatalysts have been developed to promote the hydrofunctionalisation and difunctionalisation reactions and expand substrate scope. This review provides an overview of this field, and aims at summarizing the chiral ligand used in this area of research. A detailed discussion of the development of these reactions and the general reaction mechanisms is provided.

163 citations

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TL;DR: This Account focuses on describing the origin, evolution, and synthetic applications of Pd-catalyzed asymmetric allylic C-H functionalization reactions, with an emphasis on the fundamental mechanism of the concerted proton and two-electron transfer process in allylicC-H activation.
Abstract: Asymmetric functionalization of inert C-H bonds is undoubtedly a synthetically significant yet challenging bond-forming process, allowing for the preparation of densely functionalized molecules from abundantly available feedstocks. In the past decade, our group and others have found that trivalent phosphorus ligands are capable of facilitating Pd-catalyzed allylic C-H functionalization of α-alkenes upon using p-quinone as an oxidant. In these reactions, a 16-electron Pd(0) complex bearing a monodentate phosphorus ligand, a p-quinone, and an α-alkene has been identified as a key intermediate. Through a concerted proton and two-electron transfer process, electrophilic π-allylpalladium is subsequently generated and can be leveraged to forge versatile chemical bonds with a wide range of nucleophiles. This Account focuses on describing the origin, evolution, and synthetic applications of Pd-catalyzed asymmetric allylic C-H functionalization reactions, with an emphasis on the fundamental mechanism of the concerted proton and two-electron transfer process in allylic C-H activation.Enabled by the cooperative catalysis of the palladium complex of triarylphosphine, a primary amine, and a chiral phosphoric acid, an enantioselective α-allylation of aldehydes with α-alkenes is established. The combination of chiral phosphoric acid and a palladium complex of a chiral phosphoramidite ligand allows the allylic C-H alkylation of α-alkenes with pyrazol-5-ones to give excellent enantioselectivities, wherein the chiral ligand and chiral phosphoric acid synergistically control the stereoselectivity. Notably, the palladium-phosphoramidite complexes are also efficient catalysts for allylic C-H alkylation, with a wide scope of nucleophiles. In the case of 1,4-dienes, the geometry and coordination pattern of the nucleophile are able to vary the transition states of bond-forming events and thereby determine the Z/E-, regio-, and stereoselectivities.These enantioselective allylic C-H functionalization reactions are tolerant of a wide range of nucleophiles and α-alkenes, providing a large library of optically active building blocks. Based on enantioselective intramolecular allylic C-H oxidation, the formal synthesis of (+)-diversonol is accomplished, and enantioselective intramolecular allylic C-H amination can enable concise access to letermovir. In particular, the asymmetric allylic C-H alkylation of 1,4-dienes with azlactones offers highly enantioenriched α,α-disubstituted α-amino acid derivatives that are capable of serving as key building blocks for the enantioselective synthesis of lepadiformine alkaloids. In addition, a tachykinin receptor antagonist and (-)-tanikolide are also synthesized with chiral molecules generated from the corresponding allylic C-H alkylation reactions.

90 citations