Cyclopentadienes Lewis acid catalysed

Furthermore, regioselectivities89 as well as the diastereofacial selectivities90,91 may be increased in the presence of Lewis acids (Table 8). For instance, AICI3 OEt2 improves the ewrfo-selectivity of the reaction of cyclopentadiene and methyl acrylate from 82% to 98%87. The astonishing rate accelerations, the improved yields and higher selectivities make the Lewis acid catalysed Diels-Alder reaction one of the most important organic reactions. 

The activation of various reactions by Lewis acids is now an everyday practice in synthetic organic chemistry. In contrast, solvent effects on Lewis acid catalysed Diels-Alder reactions have received much less attention. A change in the solvent can affect the association step leading to the transition structure. Ab initio calculations on the Diels-Alder reaction of cyclopentadiene and methyl vinyl ketone in aqueous media showed that there is a complex of the reactants which also involves one water molecule119. In an extreme case solvents can even impede catalysis120. The use of inert solvents such as dichloromethane and chloroform for synthetic applications of Lewis acid catalysed Diels-Alder reactions is thus well justified. General solvent effects, in particular those of water, will be discussed in the following section. 

SCHEME 8. Stereodichotomy of the Lewis acid catalysed Diels-Alder reactions of a chiral acrylic ester and cyclopentadiene... 

An extensive review of the use of chiral Lewis acid catalysts in Diels-Alder cycloadditions has been presented. Brpnsted acid-assisted chiral Lewis acids have been shown to be highly efficient catalysts for the enantioselective Diels-Alder reactions of a- and /3-substituted-Q, /i-enals with numerous dienes. The chiral Lewis acid-catalysed Diels-Alder reaction between cyclopentadiene and alkenoyloxazolidi-nones can be catalysed by bis(oxazolone)magnesium catalysts. ... 

The Lewis acid catalysed Diels-Alder cycloaddition of the ketone (4i) with cyclopentadiene allows a complete endo selectivity to be reached. Accordingly, the reaction of (4i) with 1.5 equivalents of cyclopentadiene in the presence of one equivalent of Cl2Ti(OiPr)2 in toluene at 0°C fori2 hrs led exclusively to (5i) which has been isolated in 70 % yield. In the presence of 1.5 equivalents of the oxazaborolidine derived from L-N-... 

Diels-Alder reactions are, as we know, little influenced by polar factors, such as changing the solvent from a non-polar to a polar one. Yet Lewis acids exert a strong catalysing effect. Furthermore, Lewis-acid-catalysed Diels-Alder reactions are not only faster but also more stereoselective and more regio-selective than the uncatalysed reactions. For this reason, the catalysed reactions are of great synthetic importance. Thus, cupric ion has been used249 to catalyse the Diels-Alder reaction of the 5-substituted cyclopentadiene (287), in order to... 

Asymmetric inverse-electron-demand 1,3-dipolar cycloaddition of C,A-cyclic azomethine imines with c-rich dipolarophiles was accomplished with a high stereo-selectivity by using an axially chiral dicarboxylic catalyst (40)." The metal-free silicon Lewis-acid-catalysed 3-1-2-cycloadditions of A-acylhydrazones with cyclopentadiene provides a mild access to pyrazolidine derivatives in excellent... 

A one-step Lewis acid-catalysed intermolecular 4- -3-cycloaddition of aromatic a,)3-unsaturated aldehyde and ketones (105) with epoxides (106) formed seven-membered oxacycles (107) under mild conditions (Scheme 34).The effect of oxygen-, sulfur-, and halogen-substituents on the reactivity of nitrogen-stabilized oxyallyl cations in 4- -3-cycloaddition reactions has been extensively investigated. Aza-oxyallyl cationic intermediates react with cyclopentadiene and furan via an aza-4 -I- 3-cycloaddition reaction to form bicyclic cycloadducts in moderate yields. The intramolecular formal 4- -4-cycloaddition of conjugated enynes with an e-deflcient cyclobutene (108) yielded a strained six-membered cyclic allene (109) that isomerized to a 1,3-cyclohexadiene (110). This intermediate underwent a thermal or acid-promoted six-electron electrocyclic ring opening to yield a 2,4,6-cyclooctatrienone (111) (Scheme 35). ... 

S)-5-Hydroxymethyl-2(5H)-furanone (8), derived from D-ribono-lactone, was used as an intermediate in a synthesis of the 6a-carbocycline analogue (9), with a Pauson-Khand reaction being used to build up the ring system from enyne (10) (Scheme 4). When alcohol (8) underwent Diels-Alder reaction with cyclopentadiene, either the (2S, 3R)-isomer (11) or its enantiomer could be produced by appropriate manipulation of the initial adduct face-selective Lewis-acid-catalysed Diels-Alder reactions of a,iS-unsaturated esters derived from D-mannitol could be used to produce the (R,R)-isomer (12) or its enantiomer.This chemistry was extended to give syntheses of (+)-0-santalene (13) and its enantiomer from (8) the starting material was prepared as described in Vol. 20 p.260, but a number of other papers dealing with routes to this intermediate are mentioned in the next section. 

An example is the Diels-Alder reaction of 2-methylpropenal and cyclopentadiene, catalysed by a chiral Lewis acid, which may lead to four cycloadducts. Both the relative (exo vs. endo, usually achieved by spectroscopic methods) and the absolute configuration (1 vs. 2, 3 vs. 4) have to be determined68. 

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