Ruthenium-Catalyzed Oxidative Heck Reactions

Farrington, Edward J.; Brown, John M.; Barnard, Christopher F. J.; Rowsell, E.

doi:10.1002/1521-3757(20020104)114:1<177::aid-ange177>3.0.co;2-e

Cited by 18 publications

(10 citation statements)

References 24 publications

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“…In the area of heterogeneous catalysis, various metal oxides have been investigated. [3] The most effective catalysts appear to be ironcontaining acidic zeolites [4] which at elevated temperatures are thought to yield surface-activated iron±oxo species (aoxygen). [5] These species are capable of oxygen transfer to rather inert hydrocarbons, such as benzene and methane, to yield phenol and methanol, respectively.…”

Section: Revital Ben-daniel and Ronny Neumann*mentioning

confidence: 99%

“…[1] However, the reaction with main group organometallic reagents containing elements such as boron, tin, and silicon has not been demonstrated so far. Although carbon±carbon bond formation with such main group reagents with an a,b-unsaturated carbonyl compound has been reported recently to undergo a Mizoroki±Heck-type or conjugate addition reaction with palladium, [2] rhodium, [3] and ruthenium [4] catalysts, the specific nature of the metal catalysts largely influences the reaction mechanism as well as the reaction course. Herein, we report that an iridium catalyst effects the Mizoroki±Heck-type addition/elimination reaction of a,b-unsaturated carbonyl compounds with several organosilicon reagents, and constitutes the first C À C bond formation with a main group reagent.…”

mentioning

confidence: 99%

“…[2,4] Hence, an additional oxidant such as Cu(OAc) 2 is required in the palladium-or ruthenium-catalyzed reaction. On the other hand, the iridium-catalyzed reaction proceeds without an oxidant, and the metal species would be Ir I throughout the catalytic cycle.…”

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confidence: 99%

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Iridium‐Catalyzed Mizoroki–Heck‐Type Reaction of Organosilicon Reagents

Koike

Sanada

et al. 2003

Angew Chem Int Ed

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Iridium-catalyzed CÀC bond-forming reactions have recently attracted much attention. [1] However, the reaction with main group organometallic reagents containing elements such as boron, tin, and silicon has not been demonstrated so far. Although carbon±carbon bond formation with such main group reagents with an a,b-unsaturated carbonyl compound has been reported recently to undergo a Mizoroki±Heck-type or conjugate addition reaction with palladium, [2] rhodium, [3] and ruthenium [4] catalysts, the specific nature of the metal catalysts largely influences the reaction mechanism as well as the reaction course. Herein, we report that an iridium catalyst effects the Mizoroki±Heck-type addition/elimination reaction of a,b-unsaturated carbonyl compounds with several organosilicon reagents, and constitutes the first C À C bond formation with a main group reagent. [5] The reaction of PhSi(OMe) 3 (1) with butyl acrylate (2 a) in the presence of 5 mol % of [{IrCl(cod)} 2 ] (cod ¼ 1,5-cyclooctadiene) and tetrabutylammonium fluoride (TBAF) in toluene/H 2 O (6/1) at 120 8C for 24 h afforded the addition/ elimination product 3 a in 71 % yield while the conjugate addition product 4 a was not obtained at all. This result sharply contrasts that of the related reaction with the rhodium catalyst [{RhCl(cod)} 2 ] at 608C in THF/H 2 O (6/1), which affords the conjugate adduct 4 a as the major product with high selectivity, 3 a/4 a ¼ 3/97 (Scheme 1). [6] In contrast to the combination of silicon reagent 1 and TBAF under anhydrous conditions, which is highly effective for the palladiumcatalyzed cross-coupling reaction with organic halides, [7] the rhodium-or iridium-catalyzed reaction of this combination with 2 a proceeded only very slightly without the addition of water. Table 1 summarizes the iridium-catalyzed Mizoroki± Heck-type addition/elimination reactions of several organosilicon reagents with a,b-unsaturated carbonyl compounds. Both iridium chloride and methoxide exhibited similar reactivities in the reactions with TBAF. The reaction also proceeded in THF/H 2 O at lower temperature (70 8C), although a small amount of conjugate addition product was formed (70/5). Several aryl silanes bearing a substituent on the aromatic ring also effected the reaction. Although the reaction of an ortho-substituted aryl silane was found to be slightly slower, the Mizoroki±Heck-type product was selectively obtained over the 1,4-addition product. Alkenylsilanes, which were prepared by hydrosilylation of alkynes, could also effect the reaction to afford a diene in 67 % yield.Aryl silanediols (7±9) were also found to participate in the addition/elimination reaction. By contrast to alkoxysilanes, silanediols effected the reactions without addition of TBAF and water. However, no reaction occurred when [{IrCl(cod)} 2 ] was used as the catalyst. Only [{Ir(OMe)(cod)} 2 ] was found to be an effective catalyst. Worthy of note is that the reaction with silanediols can be a halogen-free process, which is in contrast to the palladium-catalyzed Mizoroki±Heck ...

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Section: Revital Ben-daniel and Ronny Neumann*mentioning

confidence: 99%

mentioning

confidence: 99%

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Iridium‐Catalyzed Mizoroki–Heck‐Type Reaction of Organosilicon Reagents

Koike

Sanada

et al. 2003

Angew Chem Int Ed

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“…New classes of substrates for ruthenium- [222], rhodium- [223] and palladiumcatalyzed Heck-type reactions are areneboronic acids [222][223][224][225], arylstannanes [226] and arylsilanols [227] which, under oxidative or nonoxidative [224] conditions, undergo coupling with electron-deficient alkenes.…”

Section: 25mentioning

confidence: 99%

Cross‐Coupling of Organyl Halides with Alkenes: the Heck Reaction

Bräse

Meijere

2004

Metal‐Catalyzed Cross‐Coupling Reactions

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The carbopalladation of an alkene by an organylpalladium halide is the essential step in one of the major contemporary metal-catalyzed C-C-coupling reactions. About 35 years ago, a Japanese and an American group almost simultaneously designed and executed palladium-mediated coupling reactions of aryl and alkenyl halides with alkenes [1]. In subsequent investigations, Richard Heck and his group developed this reaction into a catalytic transformation and started to demonstrate its usefulness as well as its rather broad scope. The real push to utilize this powerful C-C bond-forming process, however, started only around the mid-1980s, and by now an impressive number of publications has established the meanwhile socalled Heck reaction [2] as an indispensable method in organic synthesis [3]. The applications range from the preparation of hydrocarbons, novel polymers and dyes to new advanced enantioselective syntheses of natural products and biologically active non-natural compounds. The more or less simultaneous developments of mechanistically related variants, namely the Suzuki, Stille, Hiyama, Kumada and Negishi coupling reactions (see Chapters 2, 3, 4, 12 and 15 in this book, respectively) of metallated alkenes and arenes with aryl and alkenyl halides or the metal-catalyzed formation and cycloisomerization of enynes have drawn profit from the improvement of and mechanistic insights into the Heck reaction. This, of course, also applies vice versa. Using only a catalytic amount of a palladium(0) complex or a precursor to a palladium species, the Heck reaction can bring about unprecedented structural changes, particularly when conducted intramolecularly. The full potential of this palladium-catalyzed process is still being further explored, as demonstrated by a total of 2400 relevant publications during the past 10 years, and a continuous annual growth in publications of 15 % per year. Therefore, it is appropriate to say that the Heck reaction is one of the true "power tools" in contemporary organic synthesis [4], competing favorably with the Diels-Alder reaction (25 000 references), olefin metathesis (1500 references), Wittig reaction (15 000 references), or Claisen rearrangement (15 000 references). Scheme 5-1 Mechanism of the Heck reaction [7]. Pd(OTfa) 2 , P(2-furyl) 3 , iPr 2 EtN; Pd(OTfa) 2 or Pd(F 6 -acac) 2 ] and fluorinated phosphanes [90] [91]

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“…New classes of substrates for ruthenium- [262], rhodium- [263], and palladiumcatalyzed Heck-type reactions are areneboronic acids [262][263][264][265], arylstannanes [266], and arylsilanols [267], which, under oxidative or nonoxidative [264] conditions, undergo coupling with electron-deficient alkenes.…”

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Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

Bräse¹,

Meijere²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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The carbopalladation of an alkene by an organylpalladium halide is the essential step in one of the major contemporary metal-catalyzed C-C coupling reactions. About 45 years ago, a Japanese and an American group almost simultaneously designed and executed palladium-mediated coupling reactions of aryl and alkenyl halides with alkenes [1]. In subsequent investigations, Richard Heck and his group developed this reaction into a catalytic transformation and started to demonstrate its usefulness as well as its rather broad scope. The real push to utilize this powerful C-C-bondforming process, however, started only around the mid-1980s, and by now, an impressive number of publications have established the meanwhile so-called Heck reaction [2] 1) as an indispensable method in Organic Synthesis [3][4][5][6][7]. The universal recognition of the importance of the Heck reaction and the Negishi as well as the Suzuki coupling eventually won the Nobel Prize for Richard Heck along with Ei-ichi Negishi and Akira Suzuki in 2010. The applications of the Heck reaction range from the preparation of -functionalized and unfunctionalized -hydrocarbons, novel polymers, and dyes to new advanced enantioselective syntheses of natural products and biologically active nonnatural compounds. The more or less simultaneous developments of mechanistically related variants, namely, the Kumada, Suzuki, Stille, Hiyama, and Negishi coupling reactions (Chapters 12, 2, 3, 4, and 15, respectively) of metallated alkenes and arenes with aryl and alkenyl halides or the metal-catalyzed formation and cycloisomerization of enynes have drawn profit from the improvement of and mechanistic insights into the Heck reaction. This, of course, applies vice versa as well. Using only a catalytic amount of a palladium(0) complex or a precursor to a palladium species, the Heck reaction can bring about unprecedented structural changes, particularly when conducted intramolecularly. The full potential of this palladium-catalyzed process is still being further explored as demonstrated by a total of over 7000 publications in the past 40 years by 1) The alkynylation of aryl and alkenyl halides, frequently also considered as Heck reactions, is described in Chapter 6.

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Ruthenium-Catalyzed Oxidative Heck Reactions

Cited by 18 publications

References 24 publications

Iridium‐Catalyzed Mizoroki–Heck‐Type Reaction of Organosilicon Reagents

Iridium‐Catalyzed Mizoroki–Heck‐Type Reaction of Organosilicon Reagents

Cross‐Coupling of Organyl Halides with Alkenes: the Heck Reaction

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

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