Lewis acids zirconium-BINOL

To address the design criteria listed above, Kobayashi and co-workers prepared the mildly Lewis acidic zirconium[BINOL]2 complexes 78a,b from Zr(Of-Bu)4and (i )-BINOL and theimines 76 derived from 2-aminophenol [51a, 51b, 51c, 51d] (Scheme 26). In the presence of catalytic amounts of 78a the tri-methylsilyl ketene acetal of methyl 2-methylpropanoate (77) reacted with 76a to afford the adduct 79 quantitatively and with 34% ee. The use of N-methylim-idazole (NMI) in equal amoimts markedly improved the selectivity to 70% ee as did the use of 78b which provided 79 in 90% ee. By chemical correlation the products were shown to be of the i -configuration. The reaction displayed some generality with aromatic aldimines (83-98% ee), but the one enoHzable aldi-mine gave only modest results (56% yield, 80% ee) [51e]. 

A spectacular activation of the chiral zirconium-BINOL Lewis acid complex was achieved by the addition of the (achiral ) r-butyl-calix[4]arene. Less than 2% of the catalyst were sufficient in the enantioselective allylation of various aldehydes by allyltributyltin to reach enantiomeric excesses of more than 90%, see Casolari, S. Cozzi, P. G. Orioli, P. Tagliavini, E. Umani-Ronchi, A. Chem. Commun. 1997, 2123-2124. 

Kobayashi and co-workers. used zirconium-based bromo-BINOL complex for the catalytic enantioselective Mannich-type reaction. The o-hydroxyphenyl imine 3.36 chelates the Zr(IV)(BrBINOL)2 to form the activated chiral Lewis acid complex A. The ketone acetal 3.37 reacts with the Lewis acid complex A to give the complex B. The silyl group is then transferred to the 3-amino ester to form the product 3.38 and the catalyst Zr(BrBINOL)2 is regenerated, which is ready for binding with another imine molecule (Scheme 3.16). 

This asymmetric reaction was recently improved by using a Lewis acid system of BINOL, ZrCl4(THF)2 and 4-tert-calix[4]arene prepared in situ [19bj. The modified method required only 2 % BINOL and zirconium to obtain up to 96 % ee of the homoallylalcohols. 

Catalysts (25) are the Lewis acid-Lewis base bifunctional catalysts in which Lewis acid-Al(III) moiety activates acyl iminium ion and the Lewis base (oxygen of phosphine oxide) does TMSCN, simultaneously (Scheme 5.7). Halogen atoms at the 6-position enhanced both yields and enantioselectivity in Reissert-type cyanation of the imino part of 26. However, the order for the activation is not parallel to the electronegativity of the halogen atoms and, moreover, the strong electron-withdrawing trifluoromethyl group provided unexpectedly the worst result for the activation [13]. It is not simple to explain this phenomenon only in terms of the increased Lewis acidity of the metal center. Trifluoromethylated BINOL-zirconium catalysts (28) for asymmetric hetero Diels-Alder reaction (Scheme 5.8) [14], trifluoromethylated arylphosphine-palladium catalyst (32) for asymmetric hydrosilylation (Scheme 5.9) [15], and fluorinated BINOL-zinc catalyst (35) for asymmetric phenylation (Scheme 5.10) [16] are known. 

The air stable and storable zirconium catalyst, formed from Zr(0 Bu)4, 3,3 -diiodo-l,l -binaphthalene-2,2 -diol (3,3 -l2-BINOL), -propanol and water, with the putative dimeric structure (7.33) also catalyses auft -selective asymmetric aldol reactions. While this process is beheved to proceed through an acyclic transition state, as depicted in Figure 7.2, it is postulated that the greatest steric interaction is now between the silyl enol ether substituent R3 and the bulky Lewis acid resulting in the formation of the fluft -diastereomer predominantly. 

The majority of metal-based Lewis acid catalysts used in the HDA reaction are moisture sensitive and are thus usually prepared in situ. The stable and storable zirconium-BINOL Lewis acids developed by Kobayashi and coworkers, effective in the aldol reaction (see Section 7.1) can also be used as asymmetric catalysts in the HDA reaction of aliphatic and aromatic aldehydes with dioxygenated dienes. Metal-free catalytic asymmetric HDA reactions have been developed, utilising enantiomerically pure protic molecules that activate the aldehyde component by hydrogen bonding to the carbonyl group. Rawal and coworkers have achieved up... 

The HDA reaction can also be performed using imines as dienophiles to give piperidinone derivatives as the cycloadducts. This aza-Diels-Alder process has been performed in an asymmetric fashion using a variety of enantiomerically pure metal-based Lewis acids. Early work in this area was carried out by Kobayashi and coworkers using zirconium catalysts derived from BINOL (8.150) in the cycload-dition of diene (8.123) with aryl imines derived from 2-hydroxyaniline such as (8.151). ° More recently aryl imines derived from 2-methoxyaniline (o-anisidine)... 

The third approach involves the use of a chiral Lewis acid. For this purpose, a chi-rally modified zirconium complex has been developed. By using tert-butylhydroper-oxide as the oxidant and with a ligand combination of enantiopure BINOL and (achiral) 2,2 -biphenol a bicyclic cyclobutanone derivative was converted into the corresponding lactones with an enantioselectivity up to 84% ee [338]. 

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