β-Ferrocenyl-α,β-unsaturated Ketones. II. The Reduction of β-Ferrocenyl-α,β-unsaturated Ketones and Their Relative Reactivities

Kono, Hiromichi; Ishige, Masayoshi; Sakai, Koji; Shiga, Mikio; Motoyama, Izumi; Hata, Kazuo

doi:10.1246/bcsj.43.867

Cited by 5 publications

(4 citation statements)

References 14 publications

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“…The solvent was removed under vacuum at 50 8C (from 15 mbar to 0.2 mbar) and the residue purified by flash chromatography on silica gel (petroleum ether/tert-butyl methyl ether, 2 : 1; R f 0.10). Recrystallization from diethyl ether afforded 17 as colorless crystals; yield: 265 mg (95%), mp 57 8C; IR (KBr): n Ä 3001 (m), 2939 (w), 1708 (s), 1614 (m), 1588 (w), 1515 (m), 1500 (s), 1460 (m), 1440 (s), 1405 (w), 1364 (m), 1304 (s), 1287 (w), 1263 (w), 1209 (s), 1193 (w), 1159 (s), 1114 (s), 1036 (s), 1029 (s), 841 cm À1 (w); UV (acetonitrile, c 2.19 ¥ 10 À4 mol/L): l max (log e) 201 (4.81), 230 (4.10, sh), 284 nm (3.76); 1 H NMR (CDCl 3 , 300 MHz): d 2.13 (s, 6H), 2.68 (m, 4H), 2.77 (m, 4H), 3.81 (s, 6H), 6.40 (s, 1H), 6.86 (s, 1H); 13 C NMR (CDCl 3 , 125 MHz): d 24.30 (t), 29.87 (q), 44.15 (t), 55.54 (q), 95.30 (d), 120.76 (s), 131.11 (d), 156.72 (s), 208.78 (s); MS (EI, 70 eV, 55 8C): m/z (%) 279 (8), 278 (40, M ), 222 (14), 221 (100), 77 (19), 163 (8), 151 (7), 149 (13), 147 (6), 91 (8) 2,4-Bis(2-oxobutan-4-yl)-1,3,5-trimethoxybenzene (18): A mixture of 701 mg (10.0 mmol) of MVK and 420 mg (2.50 mmol) of 12 in 10 mL of acetonitrile was cooled to 0 8C under argon. A solution 1.76 g (10.0 mmol) of 50% aqueous HBF 4 in 2 mL of acetonitrile was added slowly under vigorous stirring.…”

Section: Preparative Reactionsmentioning

confidence: 99%

“…The spectroscopic data were in accordance with the data in the literature. [14] 4-(5-Methylfuran-2-yl)penten-2-one (22): To 2.09 g (25.5 mmol) of 1 and 2.50 g (25.5 mmol) of mesityl oxide in 10 mL of acetonitrile were added 38 mg (0.5 mol %) of AuCl 3 . The selective conversion was monitored by taking small aliquots and measuring 1 H NMR spectra.…”

Section: -Ferrocenyl-2-butanone (21)mentioning

confidence: 99%

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Gold(III) Chloride‐Catalyzed Addition Reactions of Electron‐Rich Arenes to Methyl Vinyl Ketone

et al. 2003

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Section: Preparative Reactionsmentioning

confidence: 99%

Section: -Ferrocenyl-2-butanone (21)mentioning

confidence: 99%

Gold(III) Chloride‐Catalyzed Addition Reactions of Electron‐Rich Arenes to Methyl Vinyl Ketone

et al. 2003

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“…Some inforniation has been given on the features of the reduction catalyzed by precipitated nickel (1)(2)(3)(4), which is performed by 1 heating organic substrates with water in the presence of precipitated nickel (ppt-Ni in abbreviati~n).~ One of the unique characteristics , of this reaction is the fact that water is used as a hydrogen donor. In comparison with the studies on the utility and mechanism of the reaction, the stereochemistry has been examined to a lesser extent.…”

Section: Introductionmentioning

confidence: 99%

Reduction of 5α-Cholestan-3-one with Water as a Hydrogen Donor in the Presence of Precipitated Metals

Ishige¹,

Shiota²,

Ideno³

1973

Can. J. Chem.

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Reduction of 5a-cholestan-3-one with various precipitated metals using water as a hydrogen donor was investigated. Precipitated cobalt in I-BuOH and nickel in dioxane afforded 5a-cholestan-3a-ol favorably. Some multi-component precipitated metals were found to show high activity.On a examine la reduction de la 5a-cholestanone-3 par divers mttaux pricipites et utilisant de I'eau comme donneur d'hydrogene. Du cobalt prtcipite dans le f-BuOH et du nickel dans la dioxanne menent favorablement au 5a-cholestanol-3a. On a trouvk que quelques metaux pricipites contenant plusieurs composants possedent une grande activite.[Traduit par le journal]Can. J. Chem., 51,3923 (1973)

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“…The 14/3hydroxy compound 17 thus obtained in 72% yield was identical with an authentic sample16 prepared from strophanthidol (22) (comparisons of spectral data and TLC). Hydrolysis of the 19-acetate group by potassium bicarbonate afforded the 19-hydroxy compound 18 in almost quantitative yield.…”

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confidence: 99%

Studies on the synthesis of cardiotonic steroids. 4. Synthesis of strophanthidin

Yoshii¹,

Oribe²,

Tumura³

et al. 1978

J. Org. Chem.

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T h e synthesis of strophanthidin (4) starting w i t h pregnenolone acetate (1) is described. 19-Hydroxylation and introduction of a 14 double bond afforded 9, which was then transformed i n t o the cardatrienolide 13. By stepwise introduction of 50and 140-hydroxy groups, strophanthidol (22) was obtained. Conversion o f strophanthidol t o strophanthidin was successfully carried out by the oxidation w i t h chromic trioxide in hexamethylphosphoric triamide. Scheme IHo @ OH -e HO 4 3 Preparation of the 3-acetate of the dihydroxy ketone 2 is outlined in Chart I. 5-Bromo-6,19-oxidopregnenolone acetate (5) prepared from pregnenolone acetate (1) by an established methodl was brominated with 2 equiv of bromine to give the 17,21-dibromo compound 6 in 63% yield. It was then subjected to lithium bromide catalyzed dehydrobromination in N,Ndimethylformamidea to furnish the conjugated dienone 7 in 70% yield. Treatment of 7 with zinc dust in weakly acidic 2propanol at reflux temperature generated the 5 double bond? yielding the trienone 8 in 89% yield. Selective hydrogenation of the 16 double bond of 8 leading to the dienone 9 was accomplished in 82% yield by heating with triphenylstannane in toluene, a convenient method for the partial reduction of conjugated dienones developed in our laboratory.9The next task-construction of the cardatrienolide structure 13-was then performed by the reaction sequence (Chart 11) which had been developed during our digitoxigenin synthesis.9 First, the 21-methylthio derivative 10 was obtained in 44% yield by the base-catalyzed reaction of 9 with diethyl oxalate followed by the reaction of the resulting 21-oxalyl derivative with methyl thiotosylate in the presence of excess Chart I 1 -Br 5 6 c-d &LL & AcO ACO A c O Br 9 6 I a Br,, AcOH. b LiBr, DMF. C Zn, i-PrOH-AcOH. d Ph,SnH, PhMe.A new route to the unsaturated oxo ester 16, an intermediate in the Raphael synthesis of steganone (4) and its companion antileukemic lignans steganacin (1) and steganangin (2), is described. Key reactions utilized in the synthetic sequence were photochemical ring closure of a stilbenecarboxylic acid to a phenanthrene, the trimethylsilyl azide modification of the Curtius rearrangement of carboxylic acids, and a two-carbon ring expansion of a 9-phenanthrylamine with dimethyl acetylenedicarboxylate.

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β-Ferrocenyl-α,β-unsaturated Ketones. II. The Reduction of β-Ferrocenyl-α,β-unsaturated Ketones and Their Relative Reactivities

Cited by 5 publications

References 14 publications

Gold(III) Chloride‐Catalyzed Addition Reactions of Electron‐Rich Arenes to Methyl Vinyl Ketone

Gold(III) Chloride‐Catalyzed Addition Reactions of Electron‐Rich Arenes to Methyl Vinyl Ketone

Reduction of 5α-Cholestan-3-one with Water as a Hydrogen Donor in the Presence of Precipitated Metals

Studies on the synthesis of cardiotonic steroids. 4. Synthesis of strophanthidin

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