Indanone derivatives

Salto, M., Umeda, M., Enomoto, M., Hatanaka, Y., Natori, S., Yoshlhlra, K., Fukuoka, M. and Kuroyanagl, M. 1975. Cytotoxicity and carcinogenicity of pterosins and pterosides, 1-indanone derivatives and bracken fern Pteridium aquilinum). Experientia 31 824-831. 

This asymmetric phase-transfer method has been applied to enantio-selective Robinson annelation as shown in Scheme 14 (41). First, alkylation of a 1-indanone derivative with the Wichtetie reagent as a methyl vinyl ketone equivalent in the presence of p-CF3BCNB gives the S-alkylation product in 92% ee and 99% yield. With 1 -(p-trifluoro-methylbenzyl)cinchonidinium bromide, a pseudo-enantiomeric diaste-reomer of p-CF3BCNB, as catalyst, the -alkylation product is obtained in 78% ee and 99% yield. These products are readily convertible to the... 

When the reaction is performed using l,3-dichloro-2-butene as the alkyl halide, the indanone derivative 11 is formed in excellent yield (99%) and with high (92%) ee (Scheme 3.3, Eq. 1) [6]. Products of type 11 are interesting intermediates for preparation of optically active tricyclic enones, which are obtained after hydrolysis and Robinson annelation [6]. 

A. Chlorination of Optically Active 2-Substituted 1-Indanone Derivatives... 

Indanone derivatives, (II),were previously prepared by the author (2) and others (3) as illustrated in Eq. 2 ... 

Donepezil-hydrazinonicotinamide hybrids. Zurek et al. [185] synthesized donepezil-hydrazinonicotinamide hybrids by condensation between indanone derivatives and the hydrazine nicotinated moiety, with acetylcholinesterase and butyrylcholinesterase inhibitory activity. 

By analogy with results obtained from asymmetric alkylations of indanone derivatives under PTC conditions, a tt- tt interaction model between catalyst and electrophilic species is proposed (Scheme 19). 

The first breakthrough in asymmetric alkylation came in 1984 when Dolling and coworkers [14] reported a 94% ee in the phase-transfer alkylation of indanone derivatives using Cinchona alkaloids as catalysts, Eq. (2). 

The best result (99% ee) was achieved by Michael addition of an indanone derivative to methyl vinyl ketone in the presence of a chiral crown ether at -78 °C in toluene (Scheme 6) [37]. 

C-alkylation of indanone derivatives and oxindoles using cinchoma alkaloids. Alkylation ofimines, glycine derivatives, and Schiff base derivatives. 

A different stereochemical outcome is observed in the reduction of the tetracyclic indanone derivative using lithium aluminum hydride in diethyl ether to afford the rranx-alcohol (83 %)212 or the cw-alcohol in the Meerwein-Ponndorf-Verley reduction employing aluminum isopropox-ide and isopropanol (99% 212 83 %213). The stereochemistry of the products were confirmed by mass spectroscopy giving a high M+-water peak (.vyn-climination) in the case of the c/.v-al-cohol213. 

Ephedrine was used as chiral modifier of Pd in the hydrogenation of some cyclic a,y9-unsaturated ketones, tetralone and indanone derivatives, affording 50-93 % chemoselectivity for the saturated ketones and up to 36% ee [48]. Hydrogenation of the ( ) isomer was much faster and afforded higher ee than that of the (Z) isomer, though both reactions provided the same major enantiomer. 

Dioxobenzocyclobutene has also attracted interest for organic synthesis. In particular, much attention has been paid to the addition of carbon nucleophiles to the carbonyl group for transformation to naphthoquinone or indanone derivatives. Double additions of excess vinyllithium to (1,2-dioxobenzocyclo-butene)chromium complex 52 at -78 °C gave the tricarbonylchromium complex of 5,10-dioxobenzocyclooctene 53 in 87% yield without formation of simple diadduct (Eq. 38) [37]. Obviously, the product 53 was formed by a double addition of vinyllithium and subsequent anionic oxy-Cope rearrangement. 

Trimethylsilyldiazomethane smoothly reacts with (trialkyl-silyl) vinylketenes, ultimately prepared from diazoketones, in a net [4+1] annulation process to afford 2-trialkylsilylcyclopentenones in good to excellent yields (eq 68). The products are readily desi-lylated by treatment with methanesulfonic acid in methanol. An analogous reaction with (trialkylsilyl)arylketenes gives trialkyl-silyl-2-indanone derivatives (eq 69). ... 

Components The shoots contain large amounts of silicic acid in the cell walls (up to 8%). The fatty acids found in H. t. contain 23-30 C-atoms. Secondary constituents of Equisetum species include alkaloids (e.g., palustrine), numerous flavones (e.g., 6-chlo-roapigenin), and flavonols as well as their dihydro derivatives, phenol- and hydroxycinnamic acids (e.g., 2,3-0-di-( )-caffeoyl-mew-tartaric acid in E. ar-vense), indanone derivatives and novel styrylpyrones such as, e.g., equisetumpyrone. The secondary product pattern reveals interspecific and intraspecific differences whereby the latter depend on the state of development. ... 

Indazoles such as 2 provided the basis for design of semicarbazones [12] such as 3 and 5 owing to the observation that the indanone derived semicarbazones provided a good spatial match with the indazoles (Fig. 29.4.4). These compounds... 

It should be of interest to cyclize compounds [14] and [15] to give indanone derivatives. However, the treatment of [14] and [15] with a mixture of phosphoric acid and formic acid under reaction conditions that we used for Nazarov reactions gave no cyclization products. 

Akiyama developed an enantioselective fluorination of indanone-derived p-ketoesters 63 with Af-fluorobis(phenylsulfonyl)amine (NFSI, 64) with the use of ehiral phosphorie acid 62 and Na2COs (Scheme 2.38). The simultaneous formation of the sodium enolate from 63 and chiral sodium phosphate from 62 under basie eonditions was the key to achieving high yield... 

Lee et al. have developed a simple, two-step method for the synthesis of indanone derivatives 133 and 134 using an intramolecular Heck reaction of MBH adducts 132 of 2-iodobenzaldehyde in the presence of Pd(OAc)2/ (o-ToOsP/EtsN (Scheme 3.52). Interestingly, using MBH adduct derived from cyclohexenone as the substrate afforded 1-hydroxyfluorene (135) in 32% yield, presumably via a p-hydrogen elimination, dehydration and aromatiza-tion along with proton migration (Scheme 3.52). 

Indanone deriv. from kolavic acid, T37.il C14H23CIO... 

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