| 书目名称 | Organic Synthesis in Water | | 编辑 | Paul A. Grieco | | 视频video | http://file.papertrans.cn/704/703889/703889.mp4 | | 图书封面 |  | | 出版日期 | Book 1998 | | 关键词 | Claisen rearrangement; Rearrangement; organic chemistry; organic synthesis; synthesis | | 版次 | 1 | | doi | https://doi.org/10.1007/978-94-011-4950-1 | | isbn_softcover | 978-94-010-6077-6 | | isbn_ebook | 978-94-011-4950-1 | | copyright | Springer Science+Business Media New York 1998 |
| 1 |
Front Matter |
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Abstract
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| 2 |
,Diels-Alder reactions in aqueous media, |
P. P. Garner |
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Abstract
Prior to Breslow’s pioneering work in the early 1980s, the use of water as a solvent for the Diels-Alder reaction was a fairly rare occurrence. It is perhaps fitting that the earliest known example of such a reaction was actually reported by Diels and Alder themselves in 1931 [1].
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| 3 |
,Hetero Diels-Alder reactions, |
D. T. Parker |
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Abstract
Hetero Diels-Alder reactions have generally required activation of the requisite dienophile through substitution with electron-withdrawing substituents, Lewis-acid catalysis and/or the use of highly reactive dienes. These reactions, therefore, have traditionally been performed in aprotic organic solvents for the solubility and compatibility of the required reagents and catalysts. As a consequence, there are inherent limitations with respect to the scope and application of the hetero Diels-Alder reaction. Recently, the use of water as a solvent in hetero [4+2] cycloadditions has served both to complement existing methodology and to open up new reaction avenues for further synthetic exploitation. This chapter will highlight the developments over the past decade with respect to the use of water in heterocycloaddition [1] and related cycloreversion processes as well as applications in heterocyclic synthesis.
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| 4 |
,Claisen rearrangements in aqueous solution, |
J. J. Gajewski |
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Abstract
The thermal rearrangement of allyl vinyl ethers to γ,δ-unsaturated carbonyl compounds was first described by Claisen in 1912 [1]. The rearrangement of allyl phenyl ethers to .-allyl phenols was described soon thereafter [2]. Claisen later proposed that a cyclic mechanism was involved in both reactions [3]. The aromatic Claisen rearrangement was subsequently demonstrated to be intramolecular and to proceed with inversion of the allyl group; that is, the α and γ carbons of the allyl group interchange [4], The rearrangements represent an important tool in the arsenal of synthetic organic chemistry, and extensive reviews provide a wealth of data on the reactions [5]. Both the aliphatic and aromatic Claisen rearrangements involve a 3,3-sigmatropic shift [6]. That is, a bond is broken and a new bond is formed to an atom that is three atoms away along a chain from one of the atoms in the initial bond, and the new bond is formed three atoms away along the chain from the other atom that was part of the original bond. In the case of the aromatic Claisen rearrangement, a subsequent acid- or base-catalyzed tautomerization of the dienone intermediate must occur (Scheme 3.1).
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| 5 |
,Carbonyl additions and organometallic chemistry in water, |
A. Lubineau,J. Augé,Y. Queneau |
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Abstract
This chapter is devoted to aqueous carbonyl additions, with the focus on organometallic additions. Thus Barbier-type reactions in water, the success of which is increasing, are described at length in section 4.2. The subsequent section deals with conjugate additions, and section 4.4 deals with cross-aldol reactions, with special attention being paid to organometallic additions. Section 4.5 is devoted to organometallic pinacol couplings in water. Some miscellaneous reactions in which the carbonyl group is the reactive site are reviewed briefly at the end of the chapter.
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| 6 |
,Aqueous transition-metal catalysis, |
I. P. Beletskaya,A. V. Cheprakov |
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Abstract
The application of water in organic transition-metal catalysis was from its birth a spontaneous idea, and as such it is rather ill-defined. It is usual to justify research on the use of water in catalytic processes by environmental reasons. Certainly, the trend to get rid of organic solvents is quite common for modern chemical technology. More and more of both end-user products and industrial chemicals, which earlier were invariably associated with organic solvents, such as paints, varnishes, textile processing agents, etc., are now manufactured based on water. This means a decrease in the amount of uncontrolled release of toxic organic wastes into the environment, and a dramatic reduction of the hazards for both industrial personnel and consumers. It is natural to try to propagate this trend back to the reactors in which the chemicals themselves are being produced, in an attempt to make the whole chemical industry function as safely and efficiently as the most sophisticated chemical plant of Nature, the living cell.
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| 7 |
,Oxidations and reductions in water, |
F. Fringuelli,O. Piermatti,F. Pizzo |
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Abstract
Oxidation of organic compounds has probably been the most widely investigated process because it is of interest to both academic scientists and industrial technicians. Many oxidants and catalysts are known and a number of reaction conditions have been carefully investigated [1], The modern chemical industry requires selective highly efficient oxidations and environmentally sound technological processes. One way to attain these objectives is to make a rational selection of the reaction medium.
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| 8 |
,Base-catalyzed aldol- and Michael-type condensations in aqueous media, |
F. Fringuelli,O. Piermatti,F. Pizzo |
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Abstract
The aldol reaction is one of the most important ways to construct carbon-carbon bonds in organic synthesis. Nature itself seems to prefer this reaction in its biosynthetic processes, for example, in the prebiotic formation of saccharides [1]. Strictly speaking, the aldol reaction is the self-coupling of an aldehyde, having at least one active hydrogen in the α-position, to give a β-hydroxyaldehyde called an aldol (aldol addition), which sometimes dehydrates (aldol condensation).
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| 9 |
,Water-stable rare-earth Lewis-acid catalysis in aqueous and organic solvents, |
S. Kobayashi |
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Abstract
Lewis-acid-catalyzed carbon-carbon bond-forming reactions have been of great interest in organic synthesis because of their unique reactivities and selectivities, and for the mild conditions used [1]. While various kinds of Lewis-acid-promoted reactions have been developed and many have been applied in industry, these reactions must be carried out under strict anhydrous conditions. The presence of even a small amount of water stops the reaction, because most Lewis acids immediately react with water, rather than with the substrates, and decompose or deactivate. This fact has restricted the use of Lewis acids in organic synthesis.
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| 10 |
Back Matter |
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Abstract
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