Neue effiziente Mehrkomponenten-Reaktionen unter C-C-Verknüpfung zur kombinatorischen Anwendung in flüssiger und an fester Phase

Meijere, Armin de; Nüske, Hanno; Es‐Sayed, Mazen; Labahn, Thomas; Schroen, Maarten; Bräse, Stefan

doi:10.1002/(sici)1521-3757(19991216)111:24<3881::aid-ange3881>3.3.co;2-7

Cited by 3 publications

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“…This new threecomponent reaction has also been conducted on a solid support using the versatile triazene T1 linker (Scheme 8.90) [122,604]. The Heck coupling of an immobilized iodoarene 468 with bicyclopropylidene (16) in the presence of an acrylate forms a polymer-bound 4-arylspirooctenecarboxylate 469.…”

Section: Carbopalladation Reactions In Solid-phase Synthesesmentioning

confidence: 94%

“…Even when all three components were mixed with the palladium catalyst in one pot, the reaction between iodobenzene and bicyclopropylidene occurs first, and only the reactive diene 17, which is formed after a cyclopropylcarbinyl-to homoallylpalladium halide rearrangement, traps the acrylate in a Diels-Alder reaction to give the spiro[2.5]octenecarboxylate 18 as the vastly predominating product (Scheme 8.5) [121,122]. This domino Heck-Diels-Alder reaction can be performed twofold on 1,4-diiodobenzene, threefold on 1,3,5-tribromo-or 1,3,5-triiodobenzene, and even fourfold on 1,2,4,5-tetraiodobenzene [121b].…”

Section: The Alkenesmentioning

confidence: 99%

“…In some cases, Pd 2 (dba) 3 ·CHCl 3 was found to be far more effective than Pd(OAc) 2 [579]. The Heck reaction was performed on immobilized aryl halides, mostly iodides, or aryliodonium salts with soluble alkenes [122,209,210,[580][581][582][583][584][585][586][587][588][589][590] or on immobilized alkenes with soluble aryl halides [110e, 217a, [601][602][603][604][605][606] as well as with soluble aryliodonium salts [217b]. When performed on the same type of resin and with the same catalyst system, the immobilization of the aryl iodide appears to be more beneficial than that of the alkene [210].…”

Section: Carbopalladation Reactions In Solid-phase Synthesesmentioning

confidence: 99%

“…The triazene moieties upon cleavage with acid first yield diazonium salts, which in turn can be involved in the Heck reactions with various alkenes to give the additionally substituted spirooctenes 471 and 473 in good yields and excellent purities. When palladium on charcoal is employed for this transformation, the same catalyst may also serve for a subsequent catalytic hydrogenation of the double bond in the alkene-coupled product [122,604].…”

Section: Carbopalladation Reactions In Solid-phase Synthesesmentioning

confidence: 99%

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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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Section: Carbopalladation Reactions In Solid-phase Synthesesmentioning

confidence: 94%

Section: The Alkenesmentioning

confidence: 99%

Section: Carbopalladation Reactions In Solid-phase Synthesesmentioning

confidence: 99%

Section: Carbopalladation Reactions In Solid-phase Synthesesmentioning

confidence: 99%

See 2 more Smart Citations

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

Bräse¹,

Meijere²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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“…On the other hand, methylenecyclopropane derivatives with tetrasubstituted double bonds are outstandingly reactive in intramolecular Heck reactions and the particularly strained bicyclopropylidene (16) [100] in its reactivity even surpasses styrene and methyl acrylate, as demonstrated in an interesting cascade reaction of the three partners iodobenzene, bicyclopropylidene (16) and methyl acrylate. Even when all three components were mixed with the palladium catalyst in one pot, reaction between iodobenzene and bicyclopropylidene occurs first, and only the reactive diene 17, which is formed after a cyclopropylcarbinyl-to homoallylpalladium halide rearrangement, traps the acrylate in a Diels-Alder reaction to give the spiro[2.5]octenecarboxylate 18 as the vastly predominating product (Scheme 5-5) [101,102]. This domino Heck-Diels-Alder reaction can be performed two-fold on 1,4-diiodobenzene, three-fold on 1,3,5-tribromo-or 1,3,5-triiodobenzene, and even four-fold on 1,2,4,5-tetraiodobenzene [101b].…”

Section: 23mentioning

confidence: 99%

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

Bräse

Meijere

2004

Metal‐Catalyzed Cross‐Coupling Reactions

View full text Add to dashboard Cite

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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Triazenes: A Versatile Tool in Organic Synthesis

Kimball

Haley

2002

Angew. Chem. Int. Ed.

281

149

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Triazenes (RN=N-NR'R") are a class of compounds that hold much promise in preparative chemistry as they are reactive groups which are both stable and adaptable to numerous synthetic transformations. Useful to scientists in pharmacology, total synthesis, polymer technology, and the construction of novel ring systems, to name a few areas, triazenes also have a tendency to surprise chemists with new reactions and increasing applicability. This review highlights some of the recent advances and diversity possible with these types of systems.

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Neue effiziente Mehrkomponenten-Reaktionen unter C-C-Verknüpfung zur kombinatorischen Anwendung in flüssiger und an fester Phase

Cited by 3 publications

References 0 publications

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

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

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

Triazenes: A Versatile Tool in Organic Synthesis

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