Aluminum Lewis acidity

Better enantiomeric excess was obtained by using (-)-menthol-aluminum Lewis acids supported on silica gel and alumina through the aluminum atom [17]. 

A systematic NMR spectroscopic study of these adducts suggests that the steric repulsion between the trimethyl aluminum Lewis acid and the phosphane Lewis base rather than the electronic factors account for the detected changes in the P-NMR spectroscopic chemical shifts (Table 1). The change in the chemical shift (A) of the phosphanes on coordination to AlMe3 has been correlated to the... 

Numerous asymmetric reactions using chiral aluminum Lewis acids have been developed some examples are shown in Scheme 73.313-315... 

Enantioselective cydizations by radical additions to olefins have been reported and a few of them have already been discussed in Sect. 2.2.1. Cycliza-tions were performed by Nishida et al. using chiral aluminum Lewis acid... 

Oppolzer and colleagues performed pioneering work on the application of chiral sultam based dienophiles in asymmetric Diels-Alder reactions. The bomanesultam based dienophiles provided excellent de values in the Lewis acid mediated Diels-Alder reactions with a wide variety of dienes179. The efficiency of the simpler toluene-2,a-sultam based dienophiles was also studied180. Chiral auxiliary 282 proved superior to 283 and 284 in the aluminum Lewis acid catalyzed Diels-Alder reactions of its A-acryloyl derivative with cyclopentadiene, 1,3-butadiene and isoprene, affording the adducts with >90% de. 

The chiral dialuminum Lewis acid 14, which is effective as an asymmetric Diels-Alder catalyst, has been prepared from DIBAH and BINOL derivatives (Scheme 12.12). " The catalytic activity of 14 is significantly greater than that of monoaluminum reagents. The catalyst achieves high reactivity and selectivity by an intramolecular interaction of two aluminum Lewis acids. Similarly, the chiral trialuminum Lewis acid 15 is quantitatively formed from optically pure 3-(2,4,6-triisopropylphenyl)binaphthol (2 equiv) and MeaAl (3 equiv) in CH2CI2 at room temperature (Scheme 12.12). " The novel structure of 15 has been ascertained by NMR spectroscopic analysis and measurement of the methane gas evolved. Trinuclear aluminum catalyst 15 is effective for the Diels-Alder reaction of methacrolein with cyclopentadiene. Diels-Alder adducts have been obtained in 99% yield with 92% exo selectivity. Under optimum reaction conditions, the... 

Propanoyl Aluminum Lewis acid-Lewis base Propanoyl Tetrachloro-... 

The synthesis ofhaloaluminate-based ionic liquids from halide salts and aluminum Lewis acids (most commonly AIX3 X=C1, Br) can generally be split into two steps (i) fomation of the desired cation by the reaction of a trialkylamine, trialkylphosphine or dialkylsulfide with a haloalkane, and (ii) formation of the haloaluminate anion by addition of an appropriate aluminum halide to this salt (Scheme 2.1). 

Other Uses. Reagent 1 has been used for enantioselec-tive enolborination, albeit with poor (1.1 1) selectivity. Similar bis-sulfonamide-derived boron Lewis acids have been used for aldol additions, "" ester-Mannich reactions, Diels-Alder reactions, Ireland-Claisen reactions, and [2,3]-Wittig rearrangements. Similar bis-sulfonamide-derived aluminum Lewis acids have been used for aldol additions, Ehels-Alder... 

Chiral titanium and aluminum Lewis acids (465), prqrared in situ from (463) at (464), promote the addition of cyclopentadiene to N-acryolyl- and N-crotonoyl-oxazolidinones (466) (Scheme 110, Table... 

ACF is very effective catalyst for other transformations via fluorinated carboca-tions, e.g. alkenylations [12], rearrangements [13], and isomerizations [14]. The advantage of ACF in this type of chemistry could partially come from the exceedingly high affinity of aluminum for fluorine, which enables the facile generation of a carbo-cation by C-F bond cleavage in organofluorine compounds. The authors focus on this aspect of aluminum Lewis acids later in the chapter. 

The authors apphed this new concept to chemoselective functionalization of carbonyls rather than acetals [194], which is usually quite difficult to achieve because of the high reactivity of the acetal counterparts with Lewis acids. Reaction of a mixture of 1 equiv. each of acetophenone and its dimethyl acetal with ketene silyl acetal 191 under the influence of bidentate aluminum Lewis acid 188 in CH2CI2 at -78 °C for 3 h afforded aldol products 195 exclusively (88 % yield). It is worth noting that employment of dibutyltin bis(triflate) (DBTT) (10 mol%) as catalyst [195], which is quite useful for activation of aldehyde carbonyls rather than acetals, gave unsatisfactory results, producing the y3-methoxy ester preferentially (Sch. 147). 

Intramolecular version of a bidentate aluminum Lewis acid Sharma, V Simard, M. Wuest, J. D. J. Am. Chem. Soc. 1992,114, 7931. 

Chiral Aluminum Lewis Acids in Organic Synthesis... 

The earliest report of a reaction mediated by a chiral three coordinate aluminum species describes an asymmetric Meerwein-Poimdorf-Verley reduction of ketones with chiral aluminum alkoxides which resulted in low induction in the alcohol products [1]. Subsequent developments in the area were sparse until over a decade later when chiral aluminum Lewis acids began to be explored in polymerization reactions, with the first report describing the polymerization of benzofuran with catalysts prepared from and ethylaluminum dichloride and a variety of chiral compounds including /5-phenylalanine [2]. Curiously, these reports did not precipitate further studies at the time because the next development in the field did not occur until nearly two decades later when Hashimoto, Komeshima and Koga reported that a catalyst derived from ethylaluminum dichloride and menthol catalyzed the asymmetric Diels-Alder reaction shown in Sch. 1 [3,4]. This is especially curious because the discovery that a Diels-Alder reaction could be accelerated by aluminum chloride was known at the time the polymerization work appeared [5], Perhaps it was because of this long delay, that the report of this asymmetric catalytic Diels-Alder reaction was to become the inspiration for the dramatic increase in activity in this field that we have witnessed in the twenty years since its appearance. It is the intent of this review to present the development of the field of asymmetric catalytic synthesis with chiral aluminum Lewis acids that includes those reports that have appeared in the literature up to the end of 1998. This review will not cover polymerization reactions or supported reactions. The latter will appear in a separate chapter in this handbook. 

The first report of an aldol reaction mediated by a chiral aluminum Lewis acid described catalysts generated from the pinene diol 12 and the bornane amino alcohol 14 [7], The catalysts were generated by the reaction of each substrate with diethylalu-minum chloride and were evaluated in the Muikaiyama aldol reaction of the ketene acetal 7 with wo-valeraldehyde. The most successful of the two was catalyst 13 which gave the aldol adduct 8 in 66 % enantiomeric excess (ee) but only in 15 % yield with 20 mol % catalyst. Very recently, this reaction has been re-investigated with catalysts generated from type 16 bornane diols [7], The aldol reaction of ketene acetal 10 with dihydrocinnamaldehyde gave the adduct 11 in 58 % ee and 50 % yield with 100 mol % catalyst (Sch. 2). 

This section reviews the literature on asymmetric carbonyl additions and reductions mediated by chiral aluminum Lewis acids. This does not include aldol reactions, cycloaddition reactions, and ene reactions, each of which will be covered in separate sections. The earliest such carbonyl addition reaction to be reported was, along with the Muikaiyama aldol reaction of ketene acetal 7 (Sch. 2), the addition of trimethylsi-lyl cyanide to o-valeraldehyde [6]. The catalyst 13 did not result in asymmetric induction as high in this reaction as it did with the Muikaiyama aldol reaction of ketene acetal 7 with wo-valeraldehyde (Sch. 2). The cyanohydrin 45 was isolated in 65 % yield as a 66 34 mixture of enantiomers only. 

Asymmetric reduction of carbonyls has also been achieved by Dupas and coworkers by reaction of achiral NADH equivalents mediated by chiral aluminum Lewis acids [23]. They reduced methyl benzoyl formate with the dihydropyrido[2,3-h]indole 86 and chiral aluminum Lewis acids whose structures are drawn and 89 and 90 (Sch. 12). Asymmetric induction was quite low. Details of the reaction, including the conditions used, were not provided nor were the procedures used for the preparation of the chiral Lewis acids 89 and 90. 

The first asymmetric Simmons-Smith reaction with a chiral Lewis acid catalyst was introduced in 1994 by Charette and Juteau and featured a chiral boron Lewis acid prepared from tartaric acid [32]. Although this process resulted in excellent enantioselec-tivity, it would not turnover, i.e. the yield was less than 10 %. In the same year Imai, Takahashi and Kobayashi introduced a chiral aluminum Lewis acid that would catalyze the cyclopropanation of allylic aleohols with significant turnover numbers but their system did not lead to asymmetric induction as high as that resulting from the dioxaborolane catalyst [33]. The catalyst is prepared from the bis-sulfonamide 132... 

Chiral Aluminum Lewis Acids in Organic Synthesis 307 Table 10. Diels-Alder reactions with chiral aluminum catalysts 178 producing adduct 3. ... 

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