La reaction de Wittig-Horner en milieu heterogene IX. Bis aldolisation des phosphonates a partir des dialdehydes aliphatiques en milieu aqueux peu basique. Synthese de cyclenols fonctionnels.

Graff, M.; Dilaimi, A. Al; Seguineau, P.; Rambaud, M.; Villiéras, J.

doi:10.1016/s0040-4039(00)84318-x

Cited by 37 publications

(8 citation statements)

References 6 publications

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“…A round bottom flask was charged with 5-hydroxycyclopent1-ene 1-carbonitrile 47 (500 mg, 4.58 mmol, 1 equiv) and Et 3 N (1.3 mL, 9.17 mmol, 2 equiv), DMAP (56 mg, 0.45 mmol, 0.1 equiv) and THF (15 mL) were added sequentially under argon. The solution was cooled to 0 °C and benzoyl chloride (1.1 mL, 9.17 mmol, 2 equiv) was added dropwise.…”

Section: Methodsmentioning

confidence: 99%

Fragment Coupling and the Construction of Quaternary Carbons Using Tertiary Radicals Generated Fromtert-AlkylN-Phthalimidoyl Oxalates By Visible-Light Photocatalysis

et al. 2015

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The coupling of tertiary carbon radicals with alkene acceptors is an underdeveloped strategy for uniting complex carbon fragments and forming new quaternary carbons. The scope and limitations of a new approach for generating nucleophilic tertiary radicals from tertiary alcohols and utilizing these intermediates in fragment coupling reactions is described. In this method, the tertiary alcohol is first acylated to give the tert-alkyl N-phthalimidoyl oxalate, which in the presence of visible-light, catalytic Ru(bpy)3(PF6)2, and a reductant fragments to form the corresponding tertiary carbon radical. In addition to reductive coupling with alkenes, substitution reactions of tertiary radicals with allylic and vinylic halides is described. A mechanism for the generation of tertiary carbon radicals from tert-alkyl N-phthalimidoyl oxalates is proposed that is based on earlier pioneering investigations of Okada and Barton. Deuterium labeling and competition experiments reveal that the reductive radical coupling of tert-alkyl N-phthalimidoyl oxalates with electron-deficient alkenes is terminated by hydrogen-atom transfer.

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Section: Methodsmentioning

confidence: 99%

Fragment Coupling and the Construction of Quaternary Carbons Using Tertiary Radicals Generated Fromtert-AlkylN-Phthalimidoyl Oxalates By Visible-Light Photocatalysis

et al. 2015

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“…53, No. 5 First, 2-carboethoxycyclohexenol derivative 36a 29) was chosen as a substrate. When a DMF solution of 36a and allyl tosylamide 23a was stirred in the presence of 2.6 mol% of Pd 2 (dba) 3 · CHCl 3 and 5.2 mol% of (S)-BINAPO at room temperature for 3 h, the cyclohexenylamine derivative 39a was obtained in 40% yield, but the ee was only 5% (Table 5, entry 1).…”

Section: Development Of a Novel Synthetic Methods For The Chiral Indolmentioning

confidence: 99%

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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“…Figure 12 shows the synthesis route of 1,4‐phenylene vinylene‐based copolymer contatining dibenzo[ d,f ][1,3] dioxepine. The copolymerzation of monomer monomer 1 with 2 in the presence of t‐Buok in degassed THF gave the copolymer copolymer 3 under witting‐horner condition at room temperature [24]. The copolymer copolymer 3 emitted a strong deep blue fluorescence under UV irradiation and showed two PL peaks at 408 and 430 nm and a shoulder at around 457 nm in dilute solution.…”

Section: Application In Luminescence Fieldmentioning

confidence: 99%

Dibenzo[d,f][1,3] dioxepine derivatives: A review

Zhang

2011

Journal of Heterocyclic Chem

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This review presents a survey of synthetic methods and reaction mechanism of the dibenzo[d,f][1,3] dioxepine derivatives. Furthermore, the influence of the substituent groups in 6,6′‐position of dibenzo[d,f][1,3] dioxepine on their conformation is explored. The functional dibenzo[d,f][1,3] dioxepine synthetically versatiles substrate, as they can be used for synthesis of a large variety of π‐conjugated oligomer and polymer containing heterocyclic compounds, such as dibromination dibenzo[d,f][1,3] dioxepine derivative as a raw material of synthesis for organic semiconductor polymers. The synthetic and fluorescent property of π‐conjugated polymers basic on dibenzo[d,f][1,3] dioxepine also is explored. J. Heterocyclic Chem., (2012).

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La reaction de Wittig-Horner en milieu heterogene IX. Bis aldolisation des phosphonates a partir des dialdehydes aliphatiques en milieu aqueux peu basique. Synthese de cyclenols fonctionnels.

Cited by 37 publications

References 6 publications

Fragment Coupling and the Construction of Quaternary Carbons Using Tertiary Radicals Generated Fromtert-AlkylN-Phthalimidoyl Oxalates By Visible-Light Photocatalysis

Fragment Coupling and the Construction of Quaternary Carbons Using Tertiary Radicals Generated Fromtert-AlkylN-Phthalimidoyl Oxalates By Visible-Light Photocatalysis

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

Dibenzo[d,f][1,3] dioxepine derivatives: A review

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