Synthesis and evaluation of 4-alkylanilines as mammary tumor inhibiting aromatase inhibitors

Hartmann, Robert C.; Batzl, C.

doi:10.1016/0223-5234(92)90188-7

Cited by 10 publications

(5 citation statements)

References 18 publications

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“…The reaction in the presence of NaBH 4 was explored in some degree depth, since alkylanilines are of practical significance both as strong and selective aromatase inhibitors and as liquid crystals components but are presently prepared through multistep procedures such as the nitration of alkylbenzenes. The present method, based on the slow addition of NaBH 4 to the irradiated solution to maintain a constant steady-state concentration of the reducing agent, gave encouraging results with all of the alkenes tested.…”

Section: Discussionmentioning

confidence: 99%

Photoinduced, Ionic Meerwein Arylation of Olefins

et al. 2001

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Irradiation of 4-chloroaniline or of its N,N-dimethyl derivative in polar solvents generates the corresponding triplet phenyl cations. These are trapped by alkenes yielding arylated products in medium to good yields. B3LYP calculations show that the triplet cation slides with negligible activation energy to a bonded adduct with ethylene, whereas it forms only a marginally stabilized CT complex with water (chosen as a representative sigma nucleophile). The structure of the final products depends on the preferred path from the adduct cation with the alkene. In the case of aryl olefins, this deprotonates to stilbene derivatives, while, from 2,3-dimethyl-2-butene and allytrimethylsilane, allylanilines are obtained by elimination of an electrofugal group in gamma. In the case of mono- and disubstituted alkenes the cation adds chloride rather than eliminating and beta-chloroalkylanilines are obtained. The regio- and sterochemistry of the addition across the alkene are best understood with a phenonium ion structure for the adduct. The nucleophile entering in beta can be varied under conditions in which the adduct cation is trapped more efficiently than the starting phenyl cation. Thus, beta-methoxyalkylanilines are formed when the irradiation is carried out in methanol. beta-Iodoalkylanilines are obtained in acetonitrile containing iodide and unsubstituted alkylanilines in the presence of sodium borohydride. A case of intramolecular nucleophilic trapping is found with 4-pentenoic acid. The reaction is a wide-scope ionic analogue of the radicalic Meerwin arylation of olefins.

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Section: Discussionmentioning

confidence: 99%

Photoinduced, Ionic Meerwein Arylation of Olefins

et al. 2001

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“…1‐(Cyclopentylmethyl)‐ p ‐nitrobenzene (10d): 30 R f = 0.35 (hexane). IR (film): $\tilde {\nu}$ = 3103, 3077, 3048 (C=CH), 1597 (C=C), 1517, 1345 cm −1 (NO 2 ).…”

Section: Methodsmentioning

confidence: 99%

Tandem Intramolecular Carbolithiation‐Lithium/Zinc Transmetallation and Applications to Carbon−Carbon Bond‐Forming Reactions

Yus¹,

Ortiz²

2004

Eur J Org Chem

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Lithium/zinc transmetallation with the cyclic organolithium intermediate 3 (prepared by intramolecular carbolithiation of the initially formed organolithium 2) gives the corresponding organozinc intermediate 5. Copper‐ or palladium‐promoted SN2′ reactions between compound 5 and allylic or propargylic halides, as well as arylation, vinylation, benzylation, acylation, and conjugate addition to α,β‐unsaturated carbonyl compounds, afford (after hydrolysis) the expected compounds 7−15, which are not accessible directly from the organolithium precursor 3 even with transition metal catalysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…37 Phenylcyclopentane was obtained by Friedel−Crafts alkylation of benzene following a procedure reported in the literature. 39 1 H NMR (CDCl 3 , 400 MHz) δ: 7.28−7.14 (m, 5H), 3.04−2.93 (m, 1H), 2.07−2.01 (m, 2H), 1.80−1.50 (m, 6H).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Phenylcyclopentane was obtained by Friedel–Crafts alkylation of benzene following a procedure reported in the literature …”

Section: Experimental Sectionmentioning

confidence: 99%

Deciphering Reactivity and Selectivity Patterns in Aliphatic C–H Bond Oxygenation of Cyclopentane and Cyclohexane Derivatives

et al. 2021

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A kinetic, product, and computational study on the reactions of the cumyloxyl radical with monosubstituted cyclopentanes and cyclohexanes has been carried out. HAT rates, siteselectivities for C−H bond oxidation, and DFT computations provide quantitative information and theoretical models to explain the observed patterns. Cyclopentanes functionalize predominantly at C-1, and tertiary C−H bond activation barriers decrease on going from methyl-and tert-butylcyclopentane to phenylcyclopentane, in line with the computed C−H BDEs. With cyclohexanes, the relative importance of HAT from C-1 decreases on going from methyl-and phenylcyclohexane to ethyl-, isopropyl-, and tertbutylcyclohexane. Deactivation is also observed at C-2 with siteselectivity that progressively shifts to C-3 and C-4 with increasing substituent steric bulk. The site-selectivities observed in the corresponding oxidations promoted by ethyl(trifluoromethyl)dioxirane support this mechanistic picture. Comparison of these results with those obtained previously for C−H bond azidation and functionalizations promoted by the PINO radical of phenyl and tert-butylcyclohexane, together with new calculations, provides a mechanistic framework for understanding C−H bond functionalization of cycloalkanes. The nature of the HAT reagent, C−H bond strengths, and torsional effects are important determinants of site-selectivity, with the latter effects that play a major role in the reactions of oxygen-centered HAT reagents with monosubstituted cyclohexanes.

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Synthesis and evaluation of 4-alkylanilines as mammary tumor inhibiting aromatase inhibitors

Cited by 10 publications

References 18 publications

Photoinduced, Ionic Meerwein Arylation of Olefins

Photoinduced, Ionic Meerwein Arylation of Olefins

Tandem Intramolecular Carbolithiation‐Lithium/Zinc Transmetallation and Applications to Carbon−Carbon Bond‐Forming Reactions

Deciphering Reactivity and Selectivity Patterns in Aliphatic C–H Bond Oxygenation of Cyclopentane and Cyclohexane Derivatives

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