Silanes acylation

The benzoin reaction typically consists of the homocoupling of two aldehydes, which results in the formation of inherently dimeric compounds, therefore limiting the synthetic utility. The aoss-benzoin reaction has the potential to produce four products, two homocoupled adducts and two cross-benzoin products. Several strategies have been employed to develop a selective cross-benzoin reaction, including the use of donor-acceptor aldehydes, acyl silanes, acyl imines, as well as intramolecular reactions. 

In a cross-coupling benzoin condensation of two different aldehydes, usually a mixture of products is obtained, with the ratio being determined by the relative stabilities of the four possible coupling products under thermodynamic control. If, however, an acyl silane, e.g. 5, is used as the donor component, the a-silyloxy-ketone 6 is obtained as a single product " ... 

Very few optically active cyanohydrins, derived from ketones, are described in the literature. High diastcrcosclectivity is observed for the substrate-controlled addition of hydrocyanic acid to 17-oxosteroids27 and for the addition of trimethyl(2-propenyl)silane to optically active acyl cyanides28. The enantioselective hydrolysis of racemic ketone cyanohydrin esters with yeast cells of Pichia miso occurs with only moderate chemical yields20. 

Cyclopentanones from carboxylic acids by intramolecular acylation of alkyl-silanes... 

Aldehyde 106-110, 121f., 125, 144-147, 181-195, 232-236, 347ff 487f., 498, 521, 524, 5261, 544ff 557/1, 560, 599, 603ff. aus Acyl-malonsaure-diathylestcr durch re-duktive Spaltung mit Natriumboranat 195 aus N-Alkyl-nitrilium-Salzcn und Triathyl-silan 122... 

Two other examples of microwave-assisted Paal-Knorr reactions were reported in 2004, describing the synthesis of a larger set of pyrroles with different substituents around the ring. The methods differ mainly in the syntheses employed to produce the 1,4 dicarbonyl compounds required for the cyclization. A variation of the Stetter reaction between an acyl silane and dif-... 

Allylic silanes react with aldehydes, in the presence of Lewis acids, to give an allyl-substituted alcohol. In the case of benzylic silanes, this addition reaction has been induced with Mg(C104)2 under photochemical conditions. The addition of chiral additives leads to the alcohol with good asymmetric induction. In a related reaction, allylic silanes react with acyl halides to produce the corresponding carbonyl derivative. The reaction of phenyl chloroformate, trimethylallylsilane, and AICI3, for example, gave phenyl but-3-enoate. ... 

Alternative methods to access the same Breslow intermediate using NHCs utilising acyl silanes [3] or a-keto-acids have been developed [4], although these processes have not been utilised in asymmetric transformations to date. 

Enones and enoates undergo 1,2-reduction [115, 191]. Lipshutz et al. reported the effective protection of carbonyl functions by the triisopropylsilyl acyl silane group (TIPS), which allowed the selective conversion of alkenes or alkynes to the corresponding zirconocene complexes [24]. The aldehyde could subsequently be regenerated by desilylation with TBAF [186]. 

Entries 11 to 13 are examples of iminium ion and acyliminium ion reactions. Note that in Entries 11 and 12, vinyl, rather than allylic, silane moieties are involved. Entries 14 and 15 illustrate the synthesis of (3,-y-unsaturated ketones by acylation of allylic silanes. 

Entry 5 is an example of the use of fra-(trimethylsilyl)silane as the chain carrier. Entries 6 to 11 show additions of radicals from organomercury reagents to substituted alkenes. In general, the stereochemistry of these reactions is determined by reactant conformation and steric approach control. In Entry 9, for example, addition is from the exo face of the norbornyl ring. Entry 12 is an example of addition of an acyl radical from a selenide. These reactions are subject to competition from decarbonylation, but the relatively slow decarbonylation of aroyl radicals (see Part A, Table 11.3) favors addition in this case. 

Compared to the cyclic ketones, the coupling of aliphatic aldehydes to prepare 3-substituted indoles was less successful, except for phenyl acetaldehyde, which afforded 3-phenyl indole 83 in 76% yield (Scheme 4.22). The lack of imine formation or the instability of the aliphatic aldehyde towards the reaction conditions may be responsible for the inefficiency of these reactions. Therefore, a suitable aldehyde equivalent was considered. With the facile removal of a 2-trialkylsilyl group from an indole, an acyl silane was tested as a means of preparing 3-substituted indoles. Indeed, coupling of acetyl trimethylsilane with the iodoaniline 24 gave a 2 1 mixture of 2-TMS-indole 84 and indole (85) in a combined 64% yield. Evidently, the reaction conditions did lead to some desilylation. Regardless, the silyl group of 84 was quantitatively removed upon treatment with HC1 to afford indole (85). 

Kerth and Maas <1999EJ02633> have studied the reaction between (/-diazo-2-oxoalkyl)silanes and 2-acyl-l,2,3-diazaphospholes. These form the [3+2] cycloadducts 124a-l. When heated to 80-100°C, they lose molecular... 

Friedel-Crafts acylation is widely used for the production of aromatic ketones applied as intermediates in both fine chemicals and pharmaceutical industries. The reaction is carried out by using conventional homogenous catalysts, which represents significant technical and environmental problems. The present work reports the results obtained in the Friedel-Crafts acylation of aromatic substrates (anisole and 2-methoxynaphthalene) catalyzed by Beta zeolite obtained by crystallization of silanized seeds. This material exhibits hierarchical porosity and enhanced textural properties. For the anisole acylation, the catalytic activity over the conventional Beta zeolite is slightly higher than with the modified Beta material, probably due to the relatively small size of this substrate and the weaker acidity of the last sample. However, the opposite occurred in the acylation of a bulky substrate (2-methoxynaphthalene), with the modified Beta showing a higher conversion. This result is interpreted due to the presence of a hierarchical porosity in this material, which favors the accessibility to the active sites. 

The present work reports the results obtained in the Friedel-Crafts acylation of different aromatic substrates catalyzed by zeolite Beta obtained according to a novel method based on the crystallization of silanized seeds, as a way to perturb the subsequent crystal growth step and to modify the zeolite textural properties [5], The catalytic behavior of this material is compared with that of the conventional Beta zeolite. 

Both materials were tested as catalysts in the anisole acylation (Scheme 1). The conventional Beta sample showed a slightly higher activity than the Beta (PHAPTMS). At 3 hours, the conversions were 26.8 and 22.8 % for the conventional and seed silanized catalysts, respectively. This behavior is explained as a consequence of the relatively small size of the anisole molecule, which allows this compound to diffuse without significant hindrances through the zeolitic micropores, and of the slightly weaker acidity of the Beta (PHAPTMS) sample. In both cases, p-methoxyacetophenone (p-MAP) was the main reaction product, being obtained with a high selectivity (> 97%). 

The catalytic activity of hierarchical and conventional Beta zeolites for acylation of 2-MN is displayed in Figure 2(a) The Beta (PHAPTMS) sample shows a superior catalytic activity than the conventional one, due to its enhanced textural properties. In this case, the bulky nature of both substrate and products may cause the existence of diffusional problems inside the zeolitic channels, which are attenuated in the modified Beta sample due to the presence of the hierarchical porosity. Regarding the product distribution (Figure 2(b)), two main products are observed and a third isomer, 8-A,2-MN isomer is produced just in minor amounts. Interestingly, the selectivity towards the desired isomer increases in the material obtained from silanized seeds, reaching values around 75%. Probably, the active sites located on the surface of the secondary porosity are able to catalyze also the formation of 6-A,2-MN by transacylation. However, this reaction is expected to be strongly hindered in the conventional Beta zeolite since it requires the participation of two bulky molecules as reactants. 

The Beta material prepared by seed silanization show interesting catalytic properties in aromatic acylation reaction, especially when using a bulky substrate, such as 2-methoxynaphthalene. The superior activity and selectivity exhibited by this sample has been related to the presence of a hierarchical porosity, which decreases the steric and diffusional hindrances, favoring the accessibility to the active sites and allowing the occurrence of the transacylation reaction. 

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