Search results for "ylid"
showing 10 items of 1155 documents
Asymmetric synthesis of polycyclic 3-fluoroalkylproline derivatives by intramolecular azomethine ylide cycloaddition
2019
The asymmetric synthesis of polycyclic fluorinated proline derivatives has been accomplished by means of an intramolecular azomethine ylide cycloaddition with fluorinated dipolarophiles. Thus, the reaction of benzaldehydes bearing a trifluoromethyl alkene in ortho position with an azomethine ylide precursor derived from chiral 2-amino indanol takes place with excellent levels of diastereoselectivity, with simultaneous generation of four stereocenters. In order to determine the influence of the fluorine moiety in the process, starting material bearing non-fluorinated alkenes were synthesised. In this case, a dramatic drop of selectivity occurred, which indicates that the role of the fluorine…
Polar [3 + 2] cycloaddition of ketones with electrophilically activated carbonyl ylides. Synthesis of spirocyclic dioxolane indolinones
2008
International audience; The [3 + 2] cycloaddition reaction between carbonyl ylides generated from epoxides and ketones (ethyl pyruvate, ethyl phenylglyoxylate, isatin, N-methylisatin and 5-chloroisatin) to give substituted dioxolanes and spirocyclic dioxolane indolinones was investigated. The effect of microwave irradiation on the outcome of the reaction was studied. The thermal reaction between 2,2-dicyano-3-phenyloxirane and N-methylisatin was theoretically studied using DFT methods. This reaction is a domino process that comprises two steps. The first is the thermal ring opening of the epoxide to yield a carbonyl ylide intermediate, whereas the second step is a polar [3 + 2] cycloadditio…
Ylide als polymerisationsinitiatoren. I. Salzhaltige und salzfreie phosphoniumylide
1972
Phosphorylide, R3PCHX und R3PCH2·LiBr, konnen eine anionische Polymerisation von Vinylmonomeren starten. Dabei werden im Falle des Methacrylnitrils und des Methylmethacrylats die Ylide als Endgruppen in die Polymeren eingebaut. Bei den salzfreien Yliden hangt die Startwirksamkeit von der Basizitat des Ylidcarbanions ab, die Struktur dieser Ylide hat aber keinen mesbaren Einflus auf das Molekulargewicht und die Taktizitat der entstehenden Polymeren. Im Gegensatz dazu wird bei der Initiierung mit den salzhaltigen Yliden auch die Taktizitat der Polymeren von den Substituenten der Phosphorylide beeinflust. Phosphorous ylids, R3PCHX and R3PCH2·LiBr, are able to start an anionic polymerization of…
Synthesis of Photoreactive Block Copolymers Based on 1-Iminopyridinium Ylides
2010
Two photoreactive pyridinium ylide containing monomers, {[2-(metacryloyloxy)ethoxy]carbonyl}(pyridinium-1-yl)azanide (M1) and pyridinium-1-yl-(4-vinylbenzoyl)azanide (M2), were synthesized. Both monomers were polymerized under controlled radical polymerization conditions, i.e. reversible addition–fragmentation chain transfer polymerization (M1 and M2) and nitroxide-mediated polymerization (M2). Further block copolymers PMMA-b-PM1 and PS-b-PM2 were successfully synthesized and their molecular weight, Mn, and block ratio could be determined by 1H NMR analysis, thereby opening the synthetic possibilities of photoreactive ylides in block copolymer syntheses.
Polymers, Ferroelectric Liquid Crystalline Elastomers
2002
Ferroelectric materials are a subclass of pyro- and piezoelectric materials. They are very rarely found in crystalline organic or polymeric materials because ferroelectric hysteresis requires enough molecular mobility to reorient molecular dipoles in space. So semicrystalline polyvinylidene fluoride (PVDF) is nearly the only known compound. On the contrary, ferroelectric behavior is very often observed in chiral liquid crystalline materials, both low molar mass and polymeric. Ferroelectric LC-elastomers represent an interesting class of material because they combine the ordering of liquid crystalline ferroelectric phases and the rubber elasticity of polymer networks. Switching of the electr…
Ring Expansion of 1,2,3,4-Tetrahydroisoquinolines to Dibenzo[c,f]azonines. An Unexpected [1,4]-Sigmatropic Rearrangement of Nitrile-Stabilized Ammoni…
2014
When the products of a Strecker reaction of 1,2,3,4-tetrahydroisoquinolines with aromatic aldehydes are quaternized with alkyl triflates and subsequently treated with base, a ring expansion to 6,7,8,13-tetrahydro-5H-dibenzo[c,f]azonine-5-carbonitriles takes place. The nine-membered cyclic products can be obtained in good yields (78-89%) in a process involving the [1,4]-sigmatropic rearrangement of a nitrile-stabilized ammonium ylide. The reaction sequence provides a new, simple, and efficient method for the synthesis of these unusual N-heterocycles.
Toward an Understanding of the Mechanisms of the Intramolecular [5 + 2] Cycloaddition Reaction of γ-Pyrones Bearing Tethered Alkenes. A Theoretical S…
2000
The molecular mechanism for the intramolecular [5 + 2] cycloaddition reaction of β-silyloxy-γ-pyrones bearing tethered alkenes has been characterized using ab initio methods. A comparative study for this sort of cycloaddition carried out at different computational levels points out that the B3LYP/6-31G* calculations give similar barriers to those obtained with the MP3/6-31G* level. Analysis of the energetic results shows that the reaction takes place along a stepwise process: first, the migration of the neighboring silyl group to the carbonyl group of the γ-pyrone takes place to give a weak oxidopyrylium ylide intermediate, which by a subsequent concerted intramolecular [5 + 2] cycloadditi…
Synthese und13C-NMR-Spektroskopie cyclischer und acyclischer β-Phosphonioenamine
1979
Quartare Phosphoniumsalze, die auser einem Allyl- einen Alkinylrest (z. B. 1) oder einen Acylmethylrest tragen (z. B. 4–6) reagieren mit primaren Aminen zu den bisher unbekannten 1,2,3,4-Tetrahydro-1,4-azaphosphoriniumsalzen 2, 3, 8–12, 19 und 25. Die Umsetzung von 4 liefert in Abhangigkeit vom eingesetzten Amin auser 8–12 die 5-Amino-1,2,3,4-tetrahydro-3-methylphosphoriniumsalze 13–16 die im sauren Medium schnell zu 17 hydrolysieren. Als Zwischenstufen der Cyclisierung von 4 konnen die offenkettigen β-Phosphonioenamine 18, 20 und 21 isoliert werden. Die Cyclisierung von 18 zu 19 gelingt erst in Gegenwart von Triethylamin als Base. Struktur und Konfiguration der neuen Verbindungen werden mi…
ChemInform Abstract: Reaction of Diphenyldiazomethane with N-Methyloxy- and N-Ethyloxycarbonyl-N-(2,2,2-trichloroethylidene)amines.
2010
Reaction of the title imines with diphenyldiazomethane gives a Δ3-1,3,4-triazoline, which leads, after loss of dinitrogen, to a transient azomethine ylide. Subsequent elimination of ethyl or methyl chloroformate gives the unexpected 1,1-diphenyl-4,4-dichloro-2-aza-1,3-butadiene.
ChemInform Abstract: Regio- and Stereoselective Synthesis of Spiropyrrolizidines and Piperazines Through Azomethine Ylide Cycloaddition Reaction.
2016
A series of original spiropyrrolizidine derivatives has been prepared by a one-pot three-component [3 + 2] cycloaddition reaction of (E)-3-arylidene-1-phenyl-pyrrolidine-2,5-diones, l-proline, and the cyclic ketones 1H-indole-2,3-dione (isatin), indenoquinoxaline-11-one and acenaphthenequinone. We disclose an unprecedented isomerization of some spiroadducts leading to a new family of spirooxindolepyrrolizidines. Furthermore, these cycloadducts underwent retro-1,3-dipolar cycloaddition yielding unexpected regioisomers. Upon treatment of the dipolarophiles with in situ generated azomethine ylides from l-proline or acenaphthenequinone, formation of spiroadducts and unusual polycyclic fused pip…