Chalcones Subject

The AFO reaction has seen very few variations since it was first reported in 1934. However, the most significant modification was reported in 1958 by Ozawa and further elaborated by Smith and others. Prior to this modification the intermediate chalcones were purified and then subjected to hydrogen peroxide in a basic medium. With the modification, the chalcone was generated in situ, from an aldehyde and a hydroxyacetophenone, and then allowed to react with aqueous hydrogen peroxide in the presence of sodium hydroxide to deliver the flavonol. Smith and coworkers conducted a limited study to examine the scope and limitations of this modification.Flavonols were delivered in 51-67% however, no flavonols were isolated with highly reactive aldehydes such as p-nitrobenzaldehyde and when 2-hydroxy-4-methoxyacetophenone was used. 

As described earlier one of the possible products from the AFO reaction is dihydroxyflavonols. Simpson and coworkers took advantage of this outcome in their synthesis of the flavonol rhamnocitrin (23). Chalcone 24 was subjected to the typical AFO conditions to deliver dihydroxyflavonol 25. The isolated product was further subjected to hydrogen peroxide to afford flavonol 25a in 30% yield. However, treatment of 25 with bismuth acetate, generated in situ from bismuth carbonate and acetic acid, gave 25a in 77% yield for a respectable 52% overall yield over two steps. 25a was then selectively demethylated with anilinium chloride to deliver rhamnocitrin (23). 

In addition, Pfister and coworkers investigated 3-hydroxyflavone-6-carboxylic acids as histamine induced gastric secretion inhibitors. After condensing 3-acetyl-4-hydroxybenzoic acid (45) with a variety of aldehydes 46 to deliver the chalcones 47, these purified chalcones were then subjected to the standard AFO conditions to afford flavonols 48 in 51-80% yield. Subsequent alkylation of 48 with methyl iodide or isopropyl iodide followed by saponification of the corresponding esters gave the target compounds. 

Bode and co-workers rendered this transformation asymmetric allowing access to a>cyclopentenes 244 with high enantioselectivity (Table 19) [128], Optimized reaction conditions include the use of A-mesityl substituted aminoindanol derived triazo-lium catalyst 214. When chalcone and derivatives we re subjected to the reaction conditions, ax-cyclopentenes were formed selectively. Although the substrate scope is also limited to P-aryl substituted enals, cis. trans ratios of up to >20 1 are observed. 

The synthetic protocol (Scheme 11.2) toward the flavan-3-ol permethylaryl ethers is based upon the transformation of rc7ro-chalcones into 1,3-diarylpropenes. These compounds are then subjected to asymmetric dihydroxylation to give diarylpropan-l,2-diols that are used as chirons for essentially enantiopure flavan-3-ols. The protocol is demonstrated in Scheme 11.2 for the synthesis of the tetra-(9-methyl-3-(9-acetyl derivatives 61a, 61b, 62a, and 62b of (-l-)-catechin (2), (—)-e 7-catechin, (—)-epicatechin (3), and (+)-e 7-epicatechin (4). ... 

Table 16.2 lists more than 80 examples of new isoprenylated chalcones reported in the period 1992 to 2003 (see also Figure 16.7). Almost half of the compounds described here are from the Leguminosae, a trend that is also evident in earlier surveys. Other plant families that are well represented in Table 16.2 are the Moraceae and the Cannabinaceae. The literature on isoprenylated flavonoids in general has been reviewed by Barron and Ibrahim to the end of 1994 57 jjjg phenolic constituents of Glycyrrhiza species (licorice), among which are many isoprenylated chalcones, were the subject of an extensive review that includes literature published up to the end of 1996. Nomura and Hano have reviewed the literature on isoprenylated phenolic compounds of the Moraceae to the end of 1993. More recent descriptions of isoprenylated flavonoids are available for the hop plant, Humulus lupulus (Cannabinaceae),and the Moraceae genera Artocarpus and Dorstenia. ... 

The catalytic asymmetric epoxidation of electron-deficient olefins, particularly a,P-unsaturated ketones, has been the subject of numerous investigations, and as a result a number of useful methodologies have been elaborated [44], Among these, the method utilizing chiral phase-transfer catalysis occupies a unique position in terms of its practical advantages. Moreover, it also allows the highly enantioselective epoxidation of trans-a,P-unsaturated ketones, particularly chalcone. 

When dienones such as 55 are subjected to the epoxidation conditions the electron-poorer C=C double bond is selectively epoxidized. The other C=C bond can be functionalized further, for example, it can be dihydroxylated, as shown in the synthesis of the lactone 56 (Scheme 10.11) [82]. Stannyl epoxides such as 57 (Scheme 10.11, see also Table 10.8, R1 = n-Bu3Sn) can be coupled with several electrophiles [72], reduction of chalcone epoxide 58 and ring opening with alkyl aluminum compounds provides access to, e.g., the diol 59 and to phenylpropionic acids (for example 60). Tertiary epoxy alcohols such as 61 can be obtained with excellent diastereoselectivity by addition of Grignard reagents to epoxy ketones [88, 89]. 

The reaction between the acid chloride of chromone-2-carboxylic acid and ethyl ethoxymagnesioacetoacetate probably leads to the expected fi-diketone which enolizes and cyclizes spontaneously to spirofuranone(52).127 A different approach was made by Hungarian workers in their synthesis of tachrosin (53), an unusual kind of flavone isolated from Tephrosia poly-stachyoides and one of the earliest natural furanones to be isolated. They subjected an unsaturated ketone (Scheme 32) to oxidative rearrangement by thallium(III) salts, a reaction well known in chalcone chemistry, and eliminated methanol from the product to obtain the necessary starting material.128... 

Topics that have formed the subjects of reviews this year include contemporary issues in electron transport research, dynamics of bimolecular photoelectron transfer reactions, photophysical properties of functionalised fullerene derivatives, carbon-carbon bond formation via radical ions, photoinduced electron transfer processes in ketone, aldehyde, and ester synthesis, photochemical reactions between arenenitriles and benzylic donors, photo-oxidation of conjugated dienes, photoredox reactions of aromatic nitro compounds, electron transfer-mediated photochemistry of some unsaturated nitrogen-containing compounds, reactions of 02( Ag), carbon dioxide activation by aza-macrocyclic complexes, and photochromism of chalcone derivatives. ... 

The route we employed in obtaining the racemic modification of the structure assigned to salimine (19) is shown in Scheme 3 and started with the Claisen-Schmidt condensation of acetophenone 23 with aldehyde 24 [34]. The resulting chalcone (92%) was subjected to simultaneous reduction of the carbon-carbon double bond... 

Experimental Procedure for the NHC-Catalyzed Synthesis of trans-Cyclopentene 10 DBU (18 mg, 12 mol%) was added to a suspension of the 1,3-dimesityl imidazolium chloride (21 mg, 6 mol%) in 2 luL of dry THF under argon atmosphere. This was followed by the addition of cinnamaldehyde 8 (132 mg, 1 mmol) and chalcone 2 (147 mg, 0.7 mmol), and the resulting solution was stirred for 8 h at room temperature (30 °C). After the removal of the solvent, the residue was subjected to chromatography on silica gel (60-120 mesh) using a 98 2 hexane/ethyl acetate... 

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