Ester condensations Dieckmann

CLAISEN - GEUTER - DIECKMANN Ester condensation Synthesis o( open chain or cyclic p keloesters by aldol type condensation... 

Tanabe, Y. The selective Claisen and Dieckmann ester condensations promoted by dichlorobis(trifluoromethanesulfonato)titanium(IV). Bull. Chem. Soc. Jpn. 1989, 62,1917-1924. 

Burinsky, D. J., Cooks, R. G. Gas-phase Dieckmann ester condensation characterized by mass spectrometry/mass spectrometry. J. Org. Chem. 1982, 47, 4864-4869. 

Thermal degradation led to the oxo compounds including [(N02)N0)][Ti0(F3CS03)4], Tilv triflate complexes efFiciently catalyze a variety of reactions including the conversion of acetophenones to 1,3,5-triarylbenzenes,658 the nucleophilic ring opening of epoxides,659 Diels—Alder reactions,660 selective Claisen and Dieckmann ester condensations,661 esterification reactions,662 Fries rearrangements,663 homoaldol reactions,664 sequential cationic and anionic polymerizations,641 and the stereoselective synthesis of m-arabinofuranosides.606... 

Benzilic acid rearrangement Benzoin reaction (condensation) Blanc chloromethylation reaction Bouveault-Blanc reduction Bucherer hydantoin synthesis Bucherer reaction Cannizzaro reaction Claisen aldoi condensation Claisen condensation Claisen-Schmidt reaction. Clemmensen reduction Darzens glycidic ester condensation Diazoamino-aminoazo rearrangement Dieckmann reaction Diels-Alder reaction Doebner reaction Erlenmeyer azlactone synthesis Fischer indole synthesis Fischer-Speior esterification Friedel-Crafts reaction... 

Synthesis This cyclisation version of the Claisen ester condensation is sometimes called the Dieckmann Reaction. 

Triflates of titanium and tin are effective catalysts for various condensations of carbonyl compounds [I2I, 122, 123, 124, 125] Claisen and Dieckmann type condensations between ester functions proceed under mild conditions in the presence of dichlorobis(trifluoromethanesulfonyloxy)titaiiiuin(rV) and a tertiary amine (equations 59 and 60) These highly regio- and stereoselective condensations were used successfully m the synthesis of carbohydrates [122]... 

This modification has become the standard procedure for the acyloin ester condensation. By doing so, the formation of products from the otherwise competitive Dieckmann condensation (Claisen ester condensation) can be avoided. A product formed by ring closure through a Dieckmann condensation consists of a ring that is smaller by one carbon atom than the corresponding cyclic acyloin. 

Carboxylic esters 1 that have an a-hydrogen can undergo a condensation reaction upon treatment with a strong base to yield a /3-keto ester 2. This reaction is called the Claisen ester condensation or acetoacetic ester condensation, the corresponding intramolecular reaction is called the Dieckmann condensation ... 

This case study deals with an industrial Dieckmann condensation (intramolecular ester condensation Scheme 5.6) considering the laboratory and the operation scale. 

The intramolecular version of ester condensation is called the Dieckmann condensation.217 It is an important method for the formation of five- and six-membered rings and has occasionally been used for formation of larger rings. As ester condensation is reversible, product structure is governed by thermodynamic control, and in situations where more than one product can be formed, the product is derived from the most stable enolate. An example of this effect is the cyclization of the diester 25.218 Only 27 is formed, because 26 cannot be converted to a stable enolate. If 26, synthesized by another method, is subjected to the conditions of the cyclization, it is isomerized to 27 by the reversible condensation mechanism. 

The intramolecular version of ester condensation is called the Dieckmann condensation,119 It is an important method for the formation of five- and six-membered rings and has occassionally been used for formation of larger rings. Entries 3-6 in Scheme 2.13 are illustrative. 

Nucleophilic addition to C=0 (contd.) ammonia derivs., 219 base catalysis, 204, 207, 212, 216, 226 benzoin condensation, 231 bisulphite anion, 207, 213 Cannizzaro reaction, 216 carbanions, 221-234 Claisen ester condensation, 229 Claisen-Schmidt reaction, 226 conjugate, 200, 213 cyanide ion, 212 Dieckmann reaction, 230 electronic effects in, 205, 208, 226 electrons, 217 Grignard reagents, 221, 235 halide ion, 214 hydration, 207 hydride ion, 214 hydrogen bonding in, 204, 209 in carboxylic derivs., 236-244 intermediates in, 50, 219 intramolecular, 217, 232 irreversible, 215, 222 Knoevenagel reaction, 228 Lewis acids in, 204, 222 Meerwein-Ponndorf reaction, 215 MejSiCN, 213 nitroalkanes, 226 Perkin reaction, 227 pH and, 204, 208, 219 protection, 211... 

Esters of dicarboxylic acids having hydrogen on the 8 or e carbon atoms undergo intramolecular cyclisation when heated with sodium or with sodium ethoxide. This cyclisation is known as the Dieckmann reaction. It is essentially an application of the Claisen (or acetoacetic ester) condensation to the formation of a ring system the condensation occurs internally to produce a... 

The synthesis may thus be seen to be an intramolecular Claisen ester condensation, which is known as the Dieckmann reaction. The procedure is an important method for the synthesis of five- and six-membered ring systems, and the cyclic /2-keto ester product may be converted into the corresponding cyclic ketone by hydrolysis followed by decarboxylation (ketonic hydrolysis, see Section 5.8.5, p. 619). The base catalyst used in Expt 7.8 is sodium ethoxide, but sodium hydride as a 50 per cent dispersion in oil is a recommended alternative. 

The forward synthetic reaction (formulated in Expt 7.9) is thus an initial mixed Claisen ester condensation, followed by a Dieckmann cyclisation, hydrolysis and decarboxylation. Indane-l,3-dione is used for the synthesis of the trione, ninhydrin (Expt 5.99). 

Intramolecular ester condensation reactions are called Dieckmann condensations and are very useful ring-forming reactions. Examples are shown in the following equations. In the second equation the yield is only 54% if sodium ethoxide is used as the base. 

Key Mechanism 22-12 The Claisen Ester Condensation 1071 22-13 The Dieckmann Condensation A Claisen Cyclization 1074 22-14 Crossed Claisen Condensations 1074 22-15 Syntheses Using /3-Dicarbonyl Compounds 1077 22-16 The Malonic Ester Synthesis 1079 22-17 The Acetoacetic Ester Synthesis 1082 22-18 Conjugate Additions The Michael Reaction 1085 Mechanism 22-13 1,2-Addition and 1,4-Addition (Conjugate Addition) 1085... 

The Claisen ester condensation (Sections 22-12 through 22-14) (Cyclizations are the Dieckmann condensation.)... 

The intramolecular version of the Claisen ester condensation is sometimes known as the Dieckmann reaction, It provides an excellent route to heterocyclic ketones (cyclic ketones with heteroatoms in the ring very important in. . 

An example is the synthesis of ethyl a-ethoxalylpropionate (R = CH,) in 70% yield. Ethyl oxalate and ethyl succinate form ethyl a-ethoxalyl-succinate (83%). In a mixed ester condensation, the use of a more reactive ester, such as the phenyl or biphenyl ester, helps to prevent side reactions. Simple heterocyclic esters, namely, ethyl nicotinate and ethyl 8-quinolinecarboxylate, undergo the mixed ester condensation in good yields. The internal condensation of ethyl adipate to give 2-carbethoxycyclopentanone (Dieckmann reaction) is an example of cyclization (81%). ... 

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