Catalyzed Diels-Alder Reaction

Table 1.2 Asymmetric Diels-Alder reactions catalyzed by CAB catalyst 3 [5a,b ...

The Diels-Alder reaction catalyzed by this chiral titanium catalyst 31 has wide generality (Scheme 1.53, 1.54, Table 1.22, 1.23). Acryloyl- and fumaroyl-oxazolidinones react with isoprene giving cycloadducts in high optical purity. 2-Ethylthio-l,3-buta-diene can also be successfully employed as the diene [42]. 

Table 1.29 Asymmetric inverse electron demand Diels-Alder reactions catalyzed by 39 [58 ...

The Asymmetric Catalytic Diels-Alder Reaction Catalyzed by Base... 

Effect of water additive was examined in the asymmetric Diels-Alder reactions catalyzed by the J ,J -DBF0X/Ph-Ni(C104)2 complex. After addition of an appropriate amount of water to the anhydrous complex A, the reaction with an excess amount of cyclopentadiene was performed at room temperature. Enantioselectivity was as high as 93% ee for the endo cycloadduct up to five equivalents of water added and the satisfactory level of 88% ee was maintained when 10 equivalents were added. However, enantioselectivity gradually decreased with the increased amounts of water added 83 and 55% ee from 15 and 50 equivalents, respectively (Scheme 7.11). When the reaction temperature went down to -40 °C, the enantioselectivity as high as 98% ee resulted up to 15 equivalents of water additive. The effect of methanol at room temperature was even more surprising. In the presence of 15 and 100 equivalents of methanol, high levels of enantioselectivities of 88% and 83% ee, respectively, were recorded for the reactions at room temperature. 

Table 3.2 Reaction yield (%) of Diels-Alder reactions catalyzed by Sc(OTf)3 (DCM, 0°C, 10mol % cat)...

Imino Diels-Alder reactions catalyzed by indium trichloride (InCIs). Facile synthesis of quinoline and phenanthridinone derivatives [106]... 

The carbonyl Diels-Alder reaction catalyzed by bismuth(lll) chloride [112]... 

Catalytic antibody 1E9, the first catalytic antibody discovered for Diels-Alder reaction, catalyzes the cycloaddition between tetrachlorothiophene dioxide and N-ethylmaleimide (Equation 4.15) [86]. 

Table 4.22 Diels-Alder reactions catalyzed by triflic acid...

Carmona D., Pilar Lamata M., Oro, L. A. Recent Advances in Homogeneous Enantioselective Diels-Alder Reactions Catalyzed by Chiral Transition-Metal Complexes Coord. Chem. Rev. 2000 200-202 717-772... 

Keywords Lewis acids, asymmetric Diels-Alder reactions catalyzed by chiral... 

Jorgensen et al. [84] studied how solvent effects could influence the course of Diels-Alder reactions catalyzed by copper(II)-bisoxazoline. They assumed that the use of polar solvents (generally nitroalkanes) improved the activity and selectivity of the cationic copper-Lewis acid used in the hetero Diels-Alder reaction of alkylglyoxylates with dienes (Scheme 31, reaction 1). The explanation, close to that given by Evans regarding the crucial role of the counterion, is a stabilization of the dissociated ion, leading to a more defined complex conformation. They also used this reaction for the synthesis of a precursor for highly valuable sesquiterpene lactones with an enantiomeric excess superior to 99%. 

Kiindig EP, Bourdin B, Bemardinelli G (1994) Asymmetric Diels-Alder reactions catalyzed by a chiral iron Lewis acid. Angew Chem Int Ed 33 1856-1858... 

Finally, intramolecular Diels-Alder reactions, catalyzed by Lewis acids <1999TL7215> or thermally induced <1997JOC2093>, were used to obtain cyano-substituted indolizidine derivatives (Scheme 6). 

Corey, E. J. Shibata, T. Lee, T. W. Asymmetric Diels-Alder Reactions Catalyzed by a Triflic Acid Activated Chiral Oxazaborolidine. J. Am. Chem. Soc. 2002,124,3808-3809. 

Figure 7.5 Diels-Alder reaction catalyzed by a Lewis acid (LA).

Figure 8 Diels-Alder reaction catalyzed by the antibody 1E9 raised against endo-hexachloronorbornene 7 and X-ray...

Figure 9 Diels-Alder reaction catalyzed by antibody 39A11 raised against the bicyclic hapten 8.

Table 12.9 Danishefsky hetero-Diels-Alder reaction catalyzed by PMS-supported rare-earth metal complexes.

In a related transformation, Bode and co-workers have demonstrated the utility of homoenolate protonation in an azadiene Diels-Alder reaction catalyzed by aminoin-danol derived A-mesityl pre-catalyst 214 [118,119], The cyclization products 213 are obtained as a single diastereomer in excellent enantiomeric excess (Table 16). Electron-deficient enals are used in order to increase the electrophihcity and reactivity of the compounds. After protonation of the homoeneolate moiety, an inverse electron demand Diels-Alder is proposed to provide the desired cychzed product. 

Scheme 12 Diels-Alder reaction catalyzed with salt 18...

Among the various methods available for the activation of dienes in a Diels-Alder reaction, Lewis acid catalysis is certainly the most important. Our group has reported the first example of a Diels-Alder reaction catalyzed by Bi(0Tf)3xH20 (Scheme 12) [72], which showed high catalytic activity and regioselectivity in comparison to other Sc-, Ti-, Sm-, or Yb-metal-based Lewis acids, well-known for their efficient catalytic activity. Bi(OTf)3 proved to be slightly more endo-selective than Sc(OTf)3. Further, no polymerisation of dienes or dienophiles was observed. Bi(OTf)3 was also found to be superior to SnCI4 and Cu(BF4)2. 

Scheme 14 Carbonyl Diels-Alder reactions catalyzed by Bi(0Tf)3-xH20...

In striking contrast with these two previous examples of 1,3-dipolar cycloaddition catalyzed by encapsulation, the EMs calculated for particular examples of Diels-Alder reactions catalyzed by Rebek s softball [25] or by Sanders [26] cyclophane, which was selected from a dynamic combinatorial library (DCL), are lower than the actual reactant concentration calculated from the volumes of the molecular cavities. Probably, the Diels-Alder reactions have more stringent orientational requirements than the 1,3-dipolar cycloaddition. The reactants of the Diels-Alder reactions, when encapsulated or included, spend a significant amount of time in ternary complexes displaying a non-productive mutual orientation. 

Larsen, J., Rasmussen, B.S., Hazell, R.G. and Skrydstrup, T, (2004) Preparation of a novel diphosphine-palladium macrocyclic complex possessing a molecular recognition site. Oxidative addition studies. Chem, Commun., 202-203 Braunstein, P., Clerc, G. and Morise, X. (2003) Cyclopropanation and Diels-Alder reactions catalyzed by the first heterobimetallic complexes with bridging phosphinooxazoline ligands. New J. Chem., 27,68-72 Braunstein, P., Clerc, G., Morise, X., Welter, R. and Mantovani, G. (2003) Phosphinooxazolines as assembling ligands in heterometallic complexes. Dalton Trans., 1601-1605. 

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