First examples of a tosylate in the palladium-catalyzed Heck cross coupling reaction

Fu, Xiaoyong; Zhang, Shuyi; Yin, Jianhua; McAllister, Timothy L.; Jiang, Sheng; Tann, Chou-Hong; Thiruvengadam, T. K.; Zhang, Fucheng

doi:10.1016/s0040-4039(01)02240-7

Cited by 62 publications

(27 citation statements)

References 19 publications

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“…[9] Representative procedure: A mixture of tosylate 4a (4.0 g, 15 mmol), a suitable olefin H 2 C=CHZ (22 mmol), Et 3 N (3.3 mL, 24 mmol), PdA C H T U N G T R E N N U N G (OAc) 2 (50.6 mg, 0.22 mmol) and PPh 3 (59 mg, 0.22 mmol) in degazed N,N-dimethylacetamide (11 mL)/DMF (4.5 mL) was heated at 105 8C under argon for 24 h. The reaction mixture was routinely monitored by 1 H NMR. If needed, additional amounts of PdA C H T U N G T R E N N U N G (OAc) 2 /PPh 3 were added to achieve total conversion of the starting tosylate.After aqueous work-up with 0.5 N HCl, the organic layer was washed with NaHCO 3 and water and evaporated to dryness.…”

Section: Methodsmentioning

confidence: 99%

An Easy, Stereoselective Synthesis of Hexahydroisoindol‐4‐ones under Phosphine Catalysis

et al. 2011

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International audienceA new synthetic approach to hexahydroisoindol-4-ones is reported, based on the formal [3+2] cyclization reaction between N-arylsulfonylimines and cyclic conjugated dienes, under phosphine catalysis. Key substrates are 3-vinylcyclohex-2-enones with electron-withdrawing substituents (ester, amido, cyano, phosphoryl and keto groups) on the exocyclic double bond, which afford the three atom synthons for the construction of the pyrroline ring. Total syn stereoselectivity is observed in these annulations. The scope of the reaction has been demonstrated and mechanistic issues are considered, based on deuteration experiments and DFT calculations

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Section: Methodsmentioning

confidence: 99%

An Easy, Stereoselective Synthesis of Hexahydroisoindol‐4‐ones under Phosphine Catalysis

et al. 2011

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“…All of the experiments were performed at room temperature (27)(28)(29)(30) • C) under a positive pressure of nitrogen. Solvents were purchased from EM science (Merck) and distilled prior to the use.…”

Section: Methodsmentioning

confidence: 99%

Long‐chain silanes as reducing agents part 1: a facile, efficient and selective route to amine and phosphine‐stabilized active Pd‐nanoparticles

Chauhan

Ramani

et al. 2009

Applied Organom Chemis

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Recently, metal nanoparticles have found applications in various fields, which have necessitated exploration of new avenues to obtain such materials. In this publication, a hydrosilane-based reduction and characterization of resulting palladium nanoparticles is achieved using palladium acetate as nanoparticle precursor and octadecylsilane as a reducing agent. The influence of phosphine and amine ligands in the stabilization of nanoparticles is also investigated. In addition, a brief mechanistic proposal of the reduction process is also discussed.

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“…Aryl iodides, however, are more reactive than the corresponding triflates (e.g., [54]) [15]. New substitutes for alkenyl triflates are the corresponding tosylates [244] and phosphates, the latter have successfully been applied in the total synthesis of (+)-cytisine [242]. It is noteworthy that in the case of tosylates as coupling partners, an equimolar ratio of palladium(II) acetate and the added phosphine ligand is beneficial.…”

Section: The Leaving Groupsmentioning

confidence: 99%

“…It is noteworthy that in the case of tosylates as coupling partners, an equimolar ratio of palladium(II) acetate and the added phosphine ligand is beneficial. Alkenyl mesylates appear to be less suitable for Heck reactions [244]. The coupling reaction can be accelerated by applying high pressure [11,162,215,[280][281][282].…”

Section: The Leaving Groupsmentioning

confidence: 99%

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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First examples of a tosylate in the palladium-catalyzed Heck cross coupling reaction

Cited by 62 publications

References 19 publications

An Easy, Stereoselective Synthesis of Hexahydroisoindol‐4‐ones under Phosphine Catalysis

An Easy, Stereoselective Synthesis of Hexahydroisoindol‐4‐ones under Phosphine Catalysis

Long‐chain silanes as reducing agents part 1: a facile, efficient and selective route to amine and phosphine‐stabilized active Pd‐nanoparticles

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

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