Decarbonylative Silylation of Esters by Combined Nickel and Copper Catalysis for the Synthesis of Arylsilanes and Heteroarylsilanes

Guo, Lin; Chatupheeraphat, Adisak; Rueping, Magnus

doi:10.1002/ange.201604696

Cited by 38 publications

(5 citation statements)

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“…This led to the development of a decarbonylative silylation reaction, under combined nickel and copper catalysis (Scheme 12). 49 After a series of attempts we found that silylborane compounds were efficient silicon nucleophiles due to their high reactivity and remarkable potential in copper-catalyzed transmetalations. 50 Even at high temperature, various esters can be successfully coupled with silylborane compounds to give arylsilanes or heteroarylsilanes with excellent functional group tolerance.…”

Section: Decarbonylative C−si Bond Forming Reactionsmentioning

confidence: 99%

Decarbonylative Cross-Couplings: Nickel Catalyzed Functional Group Interconversion Strategies for the Construction of Complex Organic Molecules

2018

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The utilization of carboxylic acid esters as electrophiles in metal-catalyzed cross-coupling reactions is increasingly popular, as environmentally friendly and readily available ester derivatives can be powerful alternatives to the commonly used organohalides. However, key challenges associated with the use of these chemicals remain to be addressed, including the stability of ester substrates and the high energy barrier associated with their oxidative addition to low-valent metal species. Due to recent developments in nickel catalysis that make it easier to perform oxidative additions, chemists have become interested in applying less reactive electrophiles as coupling counterparts in nickel-catalyzed transformations. Hence, our group and others have independently investigated various ester group substitutions and functionalizations enabled by nickel catalysis. Such methods are of great interest as they enable the exchange of ester groups, which can be used as directing groups in metal-catalyzed C-H functionalizations prior to their replacement. Here, we summarize our recent efforts toward the development of nickel-catalyzed decarbonylative cross-coupling reactions of carboxylic esters. Achievements accomplished by other groups in this area are also included. To this day, a number of new transformations have been successfully developed, including decarbonylative arylations, alkylations, cyanations, silylations, borylations, aminations, thioetherifications, stannylations, and hydrogenolysis reactions. These transformations proceed via a nickel-catalyzed decarbonylative pathway and have shown a high degree of reactivity and chemoselectivity, as well as several other unique advantages in terms of substrate availability, due to the use of esters as coupling partners. Although the mechanisms of these reactions have not yet been fully understood, chemists have already provided some important insights. For example, Yamamoto explored the stoichiometric nickel-mediated decarbonylation process of esters and proposed a reaction mechanism involving a C(acyl)-O bond cleavage and a CO extrusion. Key nickel intermediates were isolated and characterized by Shi and co-workers, supporting the assumption of a nickel/ N-heterocyclic carbene-promoted C(acyl)-O bond activation and functionalization. Our combined experimental and computational study of a ligand-controlled chemoselective nickel-catalyzed cross-coupling of aromatic esters with alkylboron reagents provided further insight into the reaction mechanism. We demonstrated that nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step, resulting in decarbonylative alkylations, while nickel complexes with monodentate phosphorus ligands promote the activation of the C(acyl)-O bond, leading to the production of ketone products. Although more detailed mechanistic investigations need to be undertaken, the successful development of decarbonylative cross-coupling reactions can serve as a solid foundation for future studies. We believe that ...

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Section: Decarbonylative C−si Bond Forming Reactionsmentioning

confidence: 99%

Decarbonylative Cross-Couplings: Nickel Catalyzed Functional Group Interconversion Strategies for the Construction of Complex Organic Molecules

2018

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“…This compound was chosen as the model substrate because of its structure, containing both ester3233343536373839 and amide group, and selective activation of amide C–N bond was very meaningful. In the presence of 10 mol% Ni(COD) 2 , 20 mol% ICy·HCl, 20 mol% NaO t Bu and 3.0 equiv K 3 PO 4 , at 130 °C under an argon atmosphere in toluene, we indeed observed the desired product 2 in 33% yield after 36 h in GC-MS (Table 1, entry 1).…”

Section: Resultsmentioning

confidence: 99%

Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins

Wang

et al. 2017

Nat Commun

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Amide and olefins are important synthetic intermediates with complementary reactivity which play a key role in the construction of natural products, pharmaceuticals and manmade materials. Converting the normally highly stable aliphatic amides into olefins directly is a challenging task. Here we show that a Ni/NHC-catalytic system has been established for decarbonylative elimination of aliphatic amides to generate various olefins via C–N and C–C bond cleavage. This study not only overcomes the acyl C–N bond activation in aliphatic amides, but also encompasses distinct chemical advances on a new type of elimination reaction called retro-hydroamidocarbonylation. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for late-stage olefination of amide groups in complex compounds.

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“…Recently, other uncommon coupling partners have also been evaluated. In 2016, the Rueping and Shi groups successfully reported the nickel‐catalyzed cross‐coupling of aryl carboxylates with Et 3 Si‐Bpin through the decarboxylation reaction, respectively. Very recently, the Feng group developed the first example of iron‐catalyzed silylation of aryl and alkenyl carbamates via C−O bond activation (Scheme ) .…”

Section: Iron‐catalyzed C−si Bond Formationmentioning

confidence: 99%

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

et al. 2020

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Carbon-heteroatom bonds are ubiquitous among pesticides, pharmaceutical agents, and natural products. In recent years, significant progress has been made in transition-metal-catalyzed carbon-heteroatom bond formation. Especially, iron-catalyzed reactions have become a focused area in organic chemistry owing to their advantages of low cost, economical and environmental benignity. This review intends to summarize the recent advances in the construction of carbon-heteroatom bonds via cross-coupling reactions using iron as a catalyst, including the formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds. A series of nucleophilic heteroatoms reagents, reaction classifications, and iron catalytic systems are discussed. In addition, some mechanistic studies have also been described. formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds are mainly focused. 2. Iron-Catalyzed CÀ N Bond Formation The construction of CÀ N bond by transition metal-catalyzed is one of the most significant transformations in organic synthesis, which is widely employed in chemical, pharmaceutical, and materials industries. [8] The classical method to access CÀ N bond is through the transition metal-catalyzed cross-coupling reaction between aryl or alkenyl halides and amines, also known as Buchwald-Hartwig amination reaction. In recent years, the formation of CÀ N bond via CÀ H activation has been welldocumented. [9] After decades of development, the great progress has been achieved in the transition metals (Cu, Pd, Ni, Fe, Co) catalyzed the construction of the CÀ N bond. [10] However, compared with other transition metals, iron-catalyzed CÀ N bond formation has less been studied, which might be caused by the negative effect of trace metals. [21-22] 2.1. Iron-Catalyzed CspÀ N Bond Formation Alkynamines are essential compounds, widely used in organic reactions such as pericyclic reaction, tandem RCM, Pauson-Khand reaction, Kinugasa reaction, Saucy-Marbet rearrangement, and Ficini-Claisen rearrangement. [11] In 2009, Zhang and coworkers [11e] developed the first example of iron-catalyzed amination of alkynyl bromides (Scheme 1). Nucleophiles such as amide, sulfonamide, and indole could react with alkynyl bromides to obtain alkynamines in high yields under FeCl 3 * 6H 2 O and DMEDA catalytic system. This reaction exhibits good functional group tolerance, and the functional groups

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Decarbonylative Silylation of Esters by Combined Nickel and Copper Catalysis for the Synthesis of Arylsilanes and Heteroarylsilanes

Cited by 38 publications

References 77 publications

Decarbonylative Cross-Couplings: Nickel Catalyzed Functional Group Interconversion Strategies for the Construction of Complex Organic Molecules

Decarbonylative Cross-Couplings: Nickel Catalyzed Functional Group Interconversion Strategies for the Construction of Complex Organic Molecules

Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

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