Epoxide asymmetric ring-opening

Dioos, B. M. L. Jacobs P. A. (2005) Impregnation of dimeric Crlll(salen) on silica and its application in epoxides asymmetric ring opening reactions.. Applied Catalysis A General, 282 181-188. 

Asymmetric ring-opening of saturated epoxides by organoctiprates has been studied, hut only low enantioselectivities f -c 1596 ee) have so far been obtained [49, 50]. Muller et al., for example, have reported that tlie reaction between cyclohexene oxide and MeMgBr, catalyzed by 1096 of a chiral Schiffhase copper complex, gave froiis-2-metliylcyclohexanol in 5096 yield and with 1096 ee [50]. 

Although the enantioselective intermolecular addition of aliphatic alcohols to meso-epoxides with (salen)metal systems has not been reported, intramolecular asymmetric ring-opening of meso-epoxy alcohols has been demonstrated. By use of monomeric cobalt acetate catalyst 8, several complex cyclic and bicydic products can be accessed in highly enantioenriched form from the readily available meso-epoxy alcohols (Scheme 7.17) [32]. 

The analogous chromium complex was used in the asymmetric ring opening of meso epoxides with trimethylsilyl azide [15] (Scheme 4). In this case a strong dependence on the anion of the ionic hquid was observed. Anions leading to hydrophobic ionic hquids, such as PFe" and SbFe", led to high... 

Asymmetric Ring Opening of Some Terminal Epoxides Catalyzed by Dimeric Type Novel Chiral Co(Salen) Complexes... 

The asymmetric ring opening (ARO) of racemic terminal epoxides with H2O via hydrolytic kinetic resolution provides an efficient synthetic route to prepare optically pure terminal epoxides. The dimeric type chiral Co(salen)AlX3 complex has great potential to catalyze HKR of terminal epoxides in a highly reactive and enantioselective manner in comparison to their monomeric analogy. 

Jacobsen et al. reported enhanced catalytic activity by cooperative effects in the asymmetric ring opening (ARO) of epoxides.[38] Chiral Co-salen complexes (Figure 4.27) were used, which were bound to different generations of commercial PAMAM dendrimers. As a direct consequence of the second-order kinetic dependence on the [Co(salen)] complex concentration of the hydrolytic kinetic resolution (HKR), reduction of the catalyst loading using monomeric catalyst leads to a sharp decrease in overall reaction rate. 

Several methods have been developed for the synthesis of the taxol side chain. We present here the asymmetric construction of this molecule via asymmetric epoxidation and asymmetric ring-opening reactions, asymmetric dihydroxylation and asymmetric aminohydroxylation reaction, asymmetric aldol reactions, as well as asymmetric Mannich reactions. 

Another example of this cooperative catalysis has been presented by Konsler et al.101 in the course of their asymmetric ring-opening (ARO) study. They found that the ARO of mew-epoxides with TMS-N3, catalyzed by Cr salen compound 132, showed a second-order kinetic dependence on the catalyst.102 They then proposed that there might be cooperative, intramolecular bimetallic catalysis taking place, with one metal activating the substrate mew-epoxide and... 

Table 9. Catalytic asymmetric ring openings of symmetrical epoxides with t-BuSH (90) catalyzed by (R)-GaLB with MS 4A.

A variety of ie.so-epoxidcs could be selectively ring-opened this way with e.e. s as high as 97% [28], The azides can be converted to 1,2-amino alcohols, which are very desirable synthetic intermediates. Surprisingly, the mechanism of the ARO (asymmetric ring-opening) was more complicated than expected [29], First, it turned out that the chloride ion in Cr-salen was replaced by azide. Secondly, water was needed and HN3 rather than Me3SiN3 was the reactant nucleophile. Thirdly, the reaction rate was found to be second order in catalyst concentration, minus one in epoxide (cyclopentene oxide), and zero order in HN3 [30],... 

A very successful example for the use of dendritic polymeric supports in asymmetric synthesis was recently described by Breinbauer and Jacobsen [76]. PA-MAM-dendrimers with [Co(salen)]complexes were used for the hydrolytic kinetic resolution (HKR) of terminal epoxides. For such asymmetric ring opening reactions catalyzed by [Co(salen)]complexes, the proposed mechanism involves cooperative, bimetallic catalysis. For the study of this hypothesis, PAMAM dendrimers of different generation [G1-G3] were derivatized with a covalent salen Hgand through an amide bond (Fig. 7.22). The separation was achieved by precipitation and SEC. The catalytically active [Co "(salen)]dendrimer was subsequently obtained by quantitative oxidation with elemental iodine (Fig. 7.22). 

Typically chiral metal complexes catalyzed asymmetric ring opening of achiral / racemic and chiral epoxides with various nucleophiles conveniently produce enantioenriched 1,2-... 

Kim et al. [67] recently reported the synthesis of heterometallic chiral polymer (salen) Co-(Al, Ga, ln)Cl3 complexes 26-32 (Figure 10) and their use in the HKR of racemic epoxides. Polymeric salen catalysts showed very high reactivity and enantioselectivity at substantially lower catalyst loadings for the asymmetric ring opening of terminal epoxide to obtain the enantio-enriched products. The performance of catalysts is retained on multiple-use and do not suffer the problems of solubility and deactivation (Scheme 5). 

Figure 12. Proposed mechanism for cooperative catalysis in asymmetric ring opening of epoxide by dendimeric frame work.

Asymmetric Ring Opening Reaction of Epoxides with Trimethylsilyl Azide (TMSN3)... 

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