Highly stereospecific palladium-catalysed vinylation of vinylic halides under solid-liquid phase transfer conditions.

Jeffery, Tuyêt

doi:10.1016/s0040-4039(00)98131-0

Cited by 327 publications

(85 citation statements)

References 12 publications

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“…5 38) in the presence of K 2 CO 3 gave 40a in 49% yield. An intramolecular Heck reaction 38,39) using a palladium catalyst gave pentacyclic compound in 59% yield, of which the 1 Hand 13 C-NMR spectra agreed with those of (Ϫ)-dehydrotubifoline reported in the literature. 40 C-NMR spectra of the hydrogenation product agreed with those of (Ϫ)-tubifoline reported in the literature.…”

Section: Total Synthesis Of (؊)-Tubifoline Using Palladium-catalyzed supporting

confidence: 80%

Development of a Novel Synthetic Method for Ring Construction Using Organometallic Complexes and Its Application to the Total Syntheses of Natural Products

Mori

2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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Organometallic complexes are useful tools in synthetic organic chemistry. In particular, they play an important role in carbon-carbon bond formation. A metalacycle, i.e., a ring compound containing a transition metal, is a useful intermediate in synthetic organic chemistry. Oxidative cyclization of unsaturated hydrocarbons, such as alkene, alkyne, carbonyl compounds, or nitrile, using a low-valent transition metal is a useful reaction for synthesis of metalacycles. It is known that a metalacycle formed from a late transition metal and unsaturated hydrocarbons is not stable and is easily converted into the reductive elimination product or b-hydrogen elimination product (Eq. 1). Since the low-valent metal complex is regenerated in this reaction, the reaction proceeds with a catalytic amount of the transition metal. On the other hand, the metalacycle formed from an early transition metal and unsaturated hydrocarbons is fairly stable and can be converted into various compounds with functional groups by treatment with various agents (Eq. 2). Therefore a stoichiometric amount of the metal complex is required in this reaction.(1) (2) Negishi et al.2) and Nugent and Calabrese 3) reported the syntheses of zirconacycles 2 from diene, enyne, and diyne 1 using zirconocene (Cp 2 Zr). Hydrolysis of zirconacycle afforded the cyclized compound 3 (Chart 1).Negishi et al. also found a synthetic method of dibutylzirconocene (Cp 2 ZrBu 2 ) from zirconocenedichloride (Cp 2 ZrCl 2 ) and butyl lithium, and dibutylzirconocene is easily converted into zirconocene coordinated by a butene ligand in situ at room temperature 4) (Eq. 3).This was a great discovery in zirconium chemistry because it is difficult to isolate zirconocene with no ligand. We were interested in those results and attempted to form carbon-carbon bonds between the unsaturated hydrocarbons, such as enyne and diene, using zirconocene. Synthesis of Heterocycles Using Zirconium-Mediated Cyclization and Total Synthesis of (؊)-DendrobineThe zirconacycles 2 were easily synthesized in situ from Cp 2 ZrCl 2 and diene, enyne, or diyne 1. To a THF solution of Cp 2 ZrCl 2 and unsaturated hydrocarbon 1 was added BuLi at Ϫ78°C under argon gas, and the solution was stirred at room Organometallic complexes are useful tools in synthetic organic chemistry. We investigated a novel synthetic method for ring construction using organometallic complexes and synthesized natural products and biologically active substances using these methods. Metalacycles formed from an early transition metal and diene, enyne, and diyne are stable under the reaction conditions and they are easily converted into compounds with functional groups by the addition of various agents. We have developed a novel synthetic method of heterocycles from enyne and diene using Cp 2 ZrBu 2 . The total syntheses of (؊)-dendrobine, (؎)-mecembrane, and (؎)-mecembrine were achieved using this procedure. To synthesize these natural products as a chiral form, a novel palladium-catalyzed asymmetric allylic amination was developed, an...

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Section: Total Synthesis Of (؊)-Tubifoline Using Palladium-catalyzed supporting

confidence: 80%

Development of a Novel Synthetic Method for Ring Construction Using Organometallic Complexes and Its Application to the Total Syntheses of Natural Products

Mori

2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…Notably, it was demonstrated that this method perfectly tolerates sensitive functional groups, such as aldehyde and halogen (Scheme 19). 34 In 1997, Lemaire reported a method for the arylation of thiophenes 48 under Jeffery's conditions 35 (Scheme 20). 36,37 It was found that in thiophenes bearing an EWG at C-2, arylation occurred at C-5 regiospecifically.…”

Section: Reactions Involving Pd 0 /Pd II Manifold: Synthetic Applicatmentioning

confidence: 99%

Direct transition metal-catalyzed functionalization of heteroaromatic compounds

2007

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During the last two decades there has been considerable growth in the development of catalytic reactions capable of activating unreactive C-H bonds. These methods allow for the synthesis of complex molecules from easily available and cheaper precursors in a fewer number of steps. Naturally, the development of C-H activation methods for direct functionalization of heterocyclic molecules, invaluable building blocks for pharmaceutical and synthetic chemistry and material science, has received substantial attention as well.

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“…Lavenot et al, 40 e.g., described a protocol for Heck-reactions that they could apply for the direct arylation of activated thiophenes, using classical reaction conditions (palladium(II) acetate and tetrabutylammonium bromide). 41 Adopting this protocol for our synthetic approach, we were able to synthesize 2-(biphenyl-4-yl)-5-cyanothiophene, but the reaction yield turned out to be unsatisfactory. Thus, we tried to find a better alternative.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of functionalized thiophene/phenyl co-oligomers by direct arylation of thiophenes

Osadnik¹,

Lützen

Martens³

2014

Arkivoc

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π-Conjugated rod-like molecules have proven to be powerful candidates for the generation of well-defined nanostructures with interesting optical and optoelectrical properties. Their synthesis, however, turns out to be rather complex in some cases. Here, we have optimized the synthesis of oligomers consisting of thiophene and phenylene groups with three or four aromatic units using a direct arylation approach, which allows us to use cheap starting materials and to minimize the number of reaction steps considerably.

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Highly stereospecific palladium-catalysed vinylation of vinylic halides under solid-liquid phase transfer conditions.

Cited by 327 publications

References 12 publications

Development of a Novel Synthetic Method for Ring Construction Using Organometallic Complexes and Its Application to the Total Syntheses of Natural Products

Development of a Novel Synthetic Method for Ring Construction Using Organometallic Complexes and Its Application to the Total Syntheses of Natural Products

Direct transition metal-catalyzed functionalization of heteroaromatic compounds

Synthesis of functionalized thiophene/phenyl co-oligomers by direct arylation of thiophenes

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