Reactions of S-acetylcyanophosphites with carbonyl compounds

The reactions of S-acetylcyanophosphites with carbonyl compounds proceeds with the formation of the corresponding 1-acetoxycyanothiophosphonates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 237–238, January, 1991.     

Reactions of polyfluoroalkenylsulfenyl chlorides with carbonyl compounds

Polyfluorinated 1-fluoroalk-1-enylsulfenyl chlorides react with ketones RCOCH₂R′ to give unsaturated sulfides. The latter undergo smooth cyclization into 2-alkylidene-1,3-oxathioles in the presence of BF₃·NEt₃. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1770–1773, October, 2000.     

Reactions of stereochemically rigid diisocyanides with manganese carbonyl derivatives

The reactions of BrMn(CO)₅ with the non-chelating stereochemically rigid bidentate ligands (L-L) 1,3-, and 1,4-diisocyanobenzene, 4,4′-diisocyanobiphenyl, and 4,4′-diisocyanodiphenylmethane afford well characterized complexes of the types BrMn(CO)₄(L-L), BrMn(CO)₃(L-L)₂, and [BrMn(CO)₄]₂(L-L). Similar reactions with [RC₅H₄Mn(CO)₂NO]⁺PF₆⁻ gave mixtures of oligomers of the type [(RC₅H₄MnNO)_n(L-L)_n+1]ⁿ⁺[PF₆⁻]_n.     

Reactions of 2-methylene-3-oxoquinuclidine with carbonyl compounds

The reaction of 2-methylene3-oxoquinuclidine with ketones, -diketones, keto esters, and cyano esters was studied. Products of mono- and diaddition of the unsaturated ketone are formed in the presence of catalytic or equimolar amounts of sodium ethoxide, as well as without a catalyst (in the case of -keto esters and -diketones).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1387–1391, October, 1981.     

Reactions of 5,6-diamino-1,3-dimethyluracil with carbonyl compounds

The first step in the acid-catalyzed reaction of 5,6-diamino-1,3-dimethyluracil with carbonyl compounds is the formation of an azomethine at the 5-amino group. Chalcone derivatives undergo a further substitution; the 6-amino group is replaced by a hydroxyl group with subsequent ring closure and the formation of a 2,3-dihydro-1,5-oxazepine ring. Azomethines based on arylidenacetones forms 2,3-dihydropyrimidino[5,6-b]-1,5-diazepine derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 241–246, February, 1984.     

Reactions of cyclic sulfur ylides with some carbonyl compounds

The reaction of a six‐membered sulfonium ylide 5 with aldehydes or ketones afforded the oxirane derivatives 6a–d as a mixture of cis and trans isomers in excellent yields. In addition, the same reactions, using five‐ or six‐membered cyclic oxosulfonium ylides 7 and 11 , gave the corresponding oxirane derivatives in good yields. Moreover, the reaction of 11 with two equimolar amounts of base and 4‐hexen‐3‐one afforded the cyclooctene oxide derivative 16 with high stereoselectivity in 59% yield via a sequential Michael–Michael‐type addition of the ylide and the resulting enolate ion followed by an intramolecular Corey–Chaykovsky reaction. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:216–222, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10022     

Photolysis of organopolysilanes. Reactions of trimethylsilylphenylsilylene with carbonyl compounds

Photolysis of tris(trimethylsilyl)phenylsilane (I) in the presence of acetone, diethyl ketone and cyclohexanone resulted in formation of the respective 2,2,2-trimethylphenyldisilanyl enol ethers in moderate yields. UV-irradiation of I in the presence of methyl acrylate, followed by treatment of the reaction mixture with isopropyl alcohol, afforded methyl 3-(1′-isopropoxy-1′-phenyltrimethyldisilanyl)propionate, in addition to an adduct arising from addition of a silicon-carbon double-bonded intermediate to the carbon-carbon double bond.     

Reactions of cyclotrigermane and germylenes with carbonyl compounds: Cycloadducts and oligomers

Reactions of germylenes, generated by thermolysis of cyclotrigermanes, or of bulky germylenes, with various α‐dicarbonyl compounds are described. They proceed through a radical pathway, as confirmed by ESR measurements, to give different types of compounds. In the reaction of (Mes₂Ge)₃ with fluorenone, formation of the 2:1 ketone/germylene cycloadduct and of the oxadigermetane, resulting from a transient digermene, occurred. In the case of acenaphthene quinone, we observed the first example of cycloaddition between a digermene and an α‐diketone. The X‐ray crystal structure of the product shows a drastically distorted six‐membered ring system. The formation of oligomeric adducts was observed with parabenzoquinone. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 125–132, 1999     

Reactions of isocyanatophosphoryl difluoride with π-abundant nitrogen heterocycles and carbonyl compounds

Reactions of electron-rich nitrogen heterocycles with isocyanatophosphoryl difluoride were studied. Novel heteroylaminophosphoryl difluorides were obtained in high yields. N-Phosphorylated imines were synthesized for the first time from carbonyl compounds and phosphorus isocyanates. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 564–566, March, 2006.     

Reactions of pentafluorophenyltrimethylsilane and cyanomethyltrimethylsilane with carbonyl compounds catalyzed by cyanide anions

Treatment of pentafluorophenyltrimethylsilane (I) and cyanomethyltrimethylsilane (II) with enolizable ketones in the presence of a catalytic amount of potassium cyanide-18-crown-6 complex gave the corresponding trimethylsilyl enol ethers. The same dehydrogenative silylation of acetylacetone and benzoylacetone with silane I was extended to the preparation of 2,4-bis(trimethylsiloxy)-1,3-pentadiene and 1-phenyl-1,3 -bis(trimethylsiloxy)-1,3-butadiene, respectively. The dehydrogenative silylation of acetylacetone and benzoylacetone with dimethylbis(pentafluorophenyl)silane under the same conditions affords novel heterocyles 5-methylene-2,6-dioxa-1-silacylohex-3-enes. In the reaction studied the silylating ability of the silanes increases in the order Me₃SiCN ? Me₂Si(CN)₂ < Me₃SiCH₂CN < Me₃SiC₆F₅ ? Me₂Si(C₆F₅)₂. On the other hand, potassium cyanide-18-crown-6 complex catalyzed the addition of silane I or II to a carbonyl group of non-enolizable compounds such as benzaldehyde, crotonaldehyde, and methyl(triethylgermyl)ketene.     

Reactions of furan derivatives with aliphatic carbonyl compounds in acid medium

Sixteen new derivatives of the furan and of the 1,1-difurylmethane series were synthesized by the reactions of furan, 2-methylfuran, 2-(3′-acetoxypropyl)furan, 2-(3′-butyl)furan, 1-cyclopropyl-2-αfurylcyclopropane, and 1,1-difurylethane with saturated and α, β-unsaturated aliphatic carbonyl compounds in acid medium.     

Reactions of furan derivatives with aliphatic carbonyl compounds in acid medium

Sixteen new derivatives of the furan and of the 1,1-difurylmethane series were synthesized by the reactions of furan, 2-methylfuran, 2-(3-acetoxypropyl)furan, 2-(3-butyl)furan, 1-cyclopropyl-2-furylcyclopropane, and 1,1-difurylethane with saturated and , -unsaturated aliphatic carbonyl compounds in acid medium.     

Reactions of trialkylsilanes with alcohols and carbonyl compounds,catalyzed by fluoride anion

Conclusions In anhydrous acetonitrile the ionic potassium, cesium and tetraethylammonium fluorides catalyze the reactions of trialkylsilanes with alcohols and carbonyl compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 932–934, April, 1973.     

Cationic cobalt(I) carbonyl compounds containing complexed cyclobutadienes

The first examples of cationic carbonyl complexes of cobalt-containing substituted cyclobutadiene ligands are reported. The carbon monoxide ligands in these complexes are labile, and can be displaced by benzene.     

Synthesis of σ-platinum cyclopentadienyl derivatives of manganese and rhenium carbonyl compounds

Russian Chemical Bulletin -     

Syntheses and molecular structures of new ferrocenylacetylide-bridged binuclear cobalt carbonyl cluster compounds

The reaction of ferrocenylacetylide compounds with Co₂(CO)₈ at room temperature affords four complexes bearing ferrocenyl units with approximately tetrahedral (μ-alkyne)dicobalt moieties [R–(C≡C) _n –R′] [Co₂(CO)₆] _{n ′} [R?=?C₅H₅FeC₅H₄-C(CH₃)₂-C₅H₄FeC₅H₄, R′?=?H, n?=?1, n′?=?1 (1); R?=?C₅H₅FeC₅H₄ [ferrocenyl (Fc)], R′?=?–CH=CHCl, n?=?1, n′?=?1 (2); R?=?Fc, R′?=?Fc, n?=?2, n′?=?1 (3), n′?=?2 (4)]. The compounds were characterized by elemental analysis, IR, ¹H(¹³C) NMR, MS and single-crystal X-ray diffraction analysis. The X-ray analyses show that coordination of the carbon–carbon triple bond and the dicobalt unit result in the formation of a Co₂C₂ tetrahedral core, and the substituents on the acetylenic units show a distortion from linearity that reflects this coordination mode.