微波对烯丙基芳醚的Claisen重排反应影响研究

5种烯丙基芳醚衍生物在无溶剂、无催化剂的条件下进行Claisen重排反应,采用了微波加热和常规加热方式,比较了同等温度下微波加热和常规加热反应速率的差异.结果表明微波加热可以显著提高烯丙基苯醚Claisen重排反应的速率.反应温度为190℃时,微波加热下反应速率可提高5～10倍.微波加热是一种无催化剂、高产率的Claisen重排反应的方法.     

Base-Mediated Claisen Rearrangement of CF3-Containing Bisallyl Ethers

We have previously clarified that the strongly electron-withdrawing CF₃ group nicely affected the base-mediated proton shift of CF₃-containing propargylic or allylic alcohols to afford the corresponding α,β-unsaturated or saturated ketones, respectively, which was applied this time to the Claisen rearrangement after O-allylation of the allylic alcohols with a CF₃ group, followed by isomerization to the corresponding allyl vinyl ethers via the proton shift, enabling the desired rearrangement in a tandem fashion, or in a stepwise manner, the latter of which was proved to have attained an excellent diastereoselectivity with the aid of a palladium catalyst.     

Facile Preparation of Substituted Allenic Esters via the Ortho Ester Claisen Rearrangement

Five substituted allenic esters were prepared in good yields through the ortho ester Claisen rearrangement of primary and secondary propargyl alcohols.     

The Mechanism of the Claisen Rearrangement: Déjà Vu All Over Again

The great baseball player Yogi Berra, who is quoted in the title, succinctly described what it meant to learn something that others had long ago appreciated. The mechanism by which the enzyme chorismate mutase accelerates the Claisen rearrangement of chorismic acid has for many years perplexed and intrigued chemists and biochemists. Yet classical effects of solvents and catalysts, which were largely ignored by the chemical community, not only provided important clues about the mechanism of the enzyme, but put the Claisen rearrangement in a new perspective. Whereas chorismic acid once seemed exceptional because it rearranged so rapidly under physiological conditions, it is now clear that even allyl vinyl ether rearranges at room temperature in aqueous solution. While the ability of the enzyme to accelerate the rearrangement of chorismate by a factor of 10⁶ was once considered extraordinary, catalysis by trivalent aluminum compounds matches, and in some cases exceeds, those rate enhancements. Therefore, it really should not be surprising to learn that Nature has independently evolved several structurally distinct solutions to the design of enzyme catalysts for the rearrangement of chorismic acid.     

Synthesis of Substituted Indenes from Isovanillin via Claisen Rearrangement and Ring‐Closing Metathesis

A new synthesis of substituted indenes was studied. Based on Claisen rearrangement, Wittig reaction and ring‐closing metathesis (RCM), a series of substituted indenes was synthesized from isovanillin in good yields.     

Structure Effect of Imidazolium-Based Dicationic Ionic Liquids on Claisen Rearrangement

A large group of imidazolium-based dicationic ionic liquids (DILs) has been prepared in good yields. Thermal stability of all DILs has been determined. The effects of the reaction time, cation, imidazolium C₂–H acidity, and anion on the Claisen rearrangement of allyl phenyl ether have been investigated. Type of anion and the presence of the acidic C₂–H bond in the imidazolium moieties have proven to be essential for this reaction. The simple procedure and the possibility of avoiding the use catalysts and volatile organic solvents make this synthetic method environmentally benign and adaptable for large-scale applications.     

Synthesis of Sporochnol A,a Marine Fish Deterrent

Abstract

A synthesis of the methyl ether of the fish‐deterrent sporochnol A is described. The route involves the application of Claisen ortho‐ester rearrangement to generate the key quaternary carbon.     

A New Synthesis of Benzofurans from Phenols via Claisen Rearrangement and Ring‐Closing Metathesis

Based on Claisen rearrangement, the double bond isomerization of O‐allyl function together with the formation of O‐vinyl function in one pot, and ring‐closing metathesis (RCM), various phenols were transformed into various benzofurans in good yields.     

Synergistic Kinetic Resolution and Asymmetric Propargyl Claisen Rearrangement for the Synthesis of Chiral Allenes

The asymmetric propargyl Claisen rearrangement provides a convenient entry to chiral allene motifs. Herein, we describe the development of a kinetic resolution and asymmetric rearrangement of racemic propargyl vinyl ethers. This transformation afforded chiral allene products along with the enantiomerically enriched substrate in good yields with excellent diastereo‐ and enantioselectivity. The complete chirality transfer and facially selective rearrangement enabled the simultaneous construction of an axially chiral allenic unit and a quaternary carbon stereocenter.     

The Asymmetric Aza‐Claisen Rearrangement: Development of Widely Applicable Pentaphenylferrocenyl Palladacycle Catalysts

Systematic studies have been performed to develop highly efficient catalysts for the asymmetric aza‐Claisen rearrangement of trihaloacetimidates. Herein, we describe the stepwise development of these catalyst systems involving four different catalyst generations finally resulting in the development of a planar chiral pentaphenylferrocenyl oxazoline palladacycle. This complex is more reactive and has a broader substrate tolerance than all previously known catalyst systems for asymmetric aza‐Claisen rearrangements. Our investigations also reveal that subtle changes can have a big impact on the activity. With the enhanced catalyst activity, the asymmetric aza‐Claisen rearrangement has a very broad scope: the methodology not only allows the formation of highly enantioenriched primary allylic amines, but also secondary and tertiary amines; allylic amines with N‐substituted quaternary stereocenters are conveniently accessible as well. The reaction conditions tolerate many important functional groups, thus providing stereoselective access to valuable functionalized building blocks, for example, for the synthesis of unnatural amino acids. Our results suggest that face‐selective olefin coordination is the enantioselectivity‐determining step, which is almost exclusively controlled by the element of planar chirality.     

An Examination of the Scope and Stereochemistry of the Ireland–Claisen Rearrangement of Boron Ketene Acetals

The Ireland–Claisen rearrangement of boron ketene acetals is described. The boron ketene acetal intermediates are formed through a soft enolization that obviates the use of strong bases and the intermediacy of alkali metal enolates. Yields and diastereoselectivities of these rearrangements are very sensitive to the choice of boron reagent, even among those that have been shown to effect quantitative formation of boron ketene acetals from esters. The rearrangement occurs at room temperature for all substrates with generally high levels of stereoselectivity. In contrast to previous reports using boron triflates, the use of a commercially available boron iodide reagent allows for a wider substrate scope that extends to propionates and arylacetates, as well as the previously described α‐oxygenated esters. This work also provides insight into the dynamic nature of boron ketene acetals and the ramifications of this behavior for reactions in which they are intermediates.     

Synthesis of Chiral Crownophanes Having Two Phenolic Groups via Tandem Claisen Rearrangement and Their Chiral Recognition

Asymmetric crownophanes having a chiral binaphthyl unit and two phenolic hydroxyl groups were thermally synthesized from the corresponding macrocyclic ethers via tandem Claisen rearrangement. Circular dichroism (CD) spectroscopic studies and HPLC experiments confirmed that little racemization of these crownophanes occurred during the thermal rearrangement. The association constants for the interaction of the chiral crownophanes with the enantiomers of phenylethylamine, phenylglycinol, and phenylalaninol were determined by a ¹H NMR titration method in CD₂Cl₂. As a result, the 27 membered crownophane has some chiral recognition for phenylglycinol.     

Detection of Claisen Rearrangement Occurring in Allyl Phenyl Ether by in situ GC/MS

Itiswellknownthattheallylc0mP0undsexhibitavariety0finterestingrearrangementreacti0ns.Intheliquidphase,temPerature-inducedClaisenrearrangement,cyclizationreactionsandacid-induced0rthoClaisenrearrangementsofallylphenyletherhavebeenstUdiedextensively.'-'However,theClaisenrearrangementinthegasphasewasrepoftedonlyrecelltly,includingtheprotonatedallylphenyletherandN-allylanilineunderpositivecheITilcalionizationcondition4",thedeprotonatedallylphenylacetateanddeprotonatedallylphenyletherundernegati…     

Directed Hydrogenations and an Ireland–Claisen Rearrangement Linked to Evans–Tishchenko Chemistry: The Highly Efficient Total Synthesis of the Marine Cyclodepsipeptide Doliculide

Two new convergent total syntheses have been developed for the cytotoxic, actin microfilament‐stabilizing marine cyclodepsipeptide doliculide ( 1 ). A key strategic element of both routes is the establishment of the central stereogenic center of the characteristic polydeoxypropionate stereotriad by means of a hydroxyl‐directed catalytic hydrogenation of a trisubstituted double bond. The requisite olefin substrates were obtained through a modified Suzuki–Miyaura coupling or through Ireland–Claisen rearrangement of a propionate ester, respectively; the latter was the direct result of a highly selective Evans–Tishchenko reduction of a hydroxy ketone that had been obtained in a stereoselective Paterson aldol reaction. Doliculide ( 1 ) was finally obtained in a total number of 17 or 15 (14) linear steps, respectively, which represents a substantial improvement over previous syntheses of this highly bioactive natural product.     

Gold(I)‐Catalyzed Desymmetrization of 1,4‐Dienes by an Enantioselective Tandem Alkoxylation/Claisen Rearrangement

An enantioselective alkoxylation/Claisen rearrangement reaction was achieved by a strategic desymmetrization of 1,4‐dienes under the catalysis of (S)‐DTBM‐Segphos(AuCl)₂/AgBF₄. This reaction system was highly selective for the formation of 3,3‐rearrangement products, providing cycloheptenes with various substitutions in good yield and good to excellent enantioselectivity. This transformation was further extended to bicyclic ring substrates, providing the opportunity to easily assemble 5,6‐ and 6,7‐fused ring systems.     

Synthesis of the tricyclic dihydrofuran moiety of azadirachtin: efficient transformation of the Claisen rearrangement intermediate into a functionalized tricyclic dihydrofuran core

Azadirachtin is a C-seco limonoid, derived from the neem tree. Previously, we reported the synthesis of the right and left segments of azadirachtin, in addition to the coupling reaction of the modeled ester utilizing Claisen rearrangement. Herein we report the transformation of the modeled rearrangement product into a tricyclic dihydrofuran, which would be expected to have bioactivity against insects.     

Application of Claisen Rearrangement and Olefin Metathesis in Organic Synthesis

Several new synthetic methods to diverse polycycles and heterocycles on the basis of [3,3]‐sigmatropic rearrangement and ring‐closing metathesis as key steps are summarized. In this regard, Claisen, aza‐Claisen, and Overman rearrangements are used in combination with other popular reactions such as ring‐closing metathesis, Suzuki coupling, Diels–Alder reaction, and retro‐Diels–Alder reaction. To this end, we prepared polycycles (e.g., cyclophanes, cage molecules), heterocycles (e.g., oxepins, azapins), carbocycles, and spirocycles with the use of the above protocol.