Reaction of aminoalcohols with butadiene catalyzed by palladium complexes. Preliminary communication

The aminoalcohols 1 , react with 2 equivalents of butadiene in the presence of catalytic quantities of bis (acetylacetonato)palladium/triphenylphosphine to give exclusively the corresponding N-octadienyl amninoalcohols. In the presence of excess butadiene, subsequent O-octadienylation occurs only for N-octadienylimino-diethanol 2g , affording the monoether 4g . O-octadienylation of 2a-f and 4g can be effected by the addition of molar quantities of triethylamine to the reaction mixture.     

Reaction of α-cyanoacrylic acid catalyzed by tertiary amines

The action of pyridine on a-cyanoacrylic add leads to the rapid and quantitative formation of 2,4-dicyano-4-pentenoic add. In the presence of excess p-nitro-benzaldehyde, 1-hydroxy-1-p-nitrophenyl-2-cyano-2-butene is formed in this reaction in addition to 2,4-dicyano-4-pentenoic add.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2644–2646, November, 1989.     

Controlled alkylation of hydroxylamines with butadiene catalyzed by palladium complexes

Conclusions A method has been developed for the synthesis of N- and O-2,7-octadienyl derivatives of hydroxylamines by reaction of butadiene with hydroxylamine and its alkyl- and aryl-substituted analogs in the presence of the catalyst Pd(acac)₂-Ph₃P-AlEt₃-CF₃CO₂H in N-methylpyrrolidone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2254–2256, October, 1986.     

Telomerization of formamide with butadiene,catalyzed by palladium complexes

Conclusions It was shown that the N-2,7- and N-1,7-octadienylformamides can be obtained by the telomerization of formamide with butadiene using the four-component catalyst Pd²⁺-Ph₃P-AlEt₃-CF₃CO₂H.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khlmicheskaya, No. 3, pp. 703–704, March, 1984.     

On the mechanism of allylic alkylations catalyzed by palladium

Reults are reported indicating the intermediacy of a symmetrical π-allyl species in the alkylation of an allylic lactone. A previous report indicating that another mechanism was operative is disputed.     

Telomerization of alkane- and arenesulfonamides with butadiene catalyzed by palladium complexes

Conclusions The catalyzed (by palladium complexes) telomerization of butadiene with butane- and p-toluenesulfonamides, which leads to difficult-to-obtain N-substituted unsaturated sulfonamides in high yields, was realized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 372–376, February, 1985.     

Oxidation of unsaturated tertiary amines,amides, and imides by molecular oxygen catalyzed by palladium complexes

Conclusions Oxidation of higher unsaturated tertiary amines, amides, and imides has been carried out using PdCl₂-CuCl-CF₃COOH catalyst system and molecular oxygen, the products being the corresponding amino-, amido-, and imidoketones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimieheskaya, No. 9, pp. 2148–2151, September, 1988.     

A case for enantioselective allylic alkylation catalyzed by palladium nanoparticles

Palladium nanoparticles (4 nm, fcc) were prepared through decomposition of [Pd2(dba)3] by H2 in the presence of a chiral xylofuranoside diphosphite. These particles catalyze the allylic alkylation of rac-3-acetoxy-1,3-diphenyl-1-propene with dimethyl malonate leading to an almost total conversion of the (R) enantiomer and almost no reaction with the (S). This gives rise to 97% ee for the alkylation product and a kinetic resolution of the substrate recovered with ca. 90% ee. This behavior was compared to that of a molecular catalyst at various dilutions, and the differences between the two systems are discussed. This is the first colloidal system shown to display such a high enantioselectivity besides the well-known Pt/cinchonidine system.     

Regio- and stereospecific synthesis of allylic tertiary amines

E and Z allylic amines have been synthesised by stereo-specific elimination of Ph₂PO₂^? from pure diastereoisomers (3) and (4).     

Reaction of 2-vinylfuran with formaldehyde catalyzed by palladium complexes

Conclusion 5-Hydroxymethyl-2-vinylfuran is formed when 2-vinylfuran reacts with formaldehyde in the presence of Pd(acac)₂-PPh₃-Al(C₂H₅)₃ catalyst (1:3:4) in a 70% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 693–695, March, 1976.     

CO-oligomerization of butadiene and cyclic ketones catalyzed by palladium phosphine complexes

Palladium(0) phosphine complexes in the presence of water catalyze the co-oligomerization of butadiene and cyclic ketones to yield α-octadienyl derivatives. It is assumed that the hydrido hydroxo complex [PdH(L)₃]OH, formed through the oxidative addition of water to PdL_n(L = tertiary phosphine), is the catalytically active species. The co-oligomerization of butadiene and cyclopentanone has been studied in detail. The ligand size appears to affect the conversion of butadiene to products.     

Reaction of methyl-substituted pyrylium salts with tertiary amines

2,4,6-Trimethylpyrylium perchlorate reacts with heterocyclic compounds containing apyridine nitrogen atom and having basicities higher than 9 pK_a units (in acetonitrile) through a step involving the formation of a methylenepyran. 4-Methyl-2,6-diphenyl- and 2-methyl-4,6-diphenylpyrylium perchlorates react with benzimidazole to give 1,2-ethanediylidenebispyrans. Methyl-substituted pyrylium salts react with 2,6-diphenylpyrylium and flavylium perchlorates in the presence of benzimidazole to give methylidynecyanines and with acetic anhydride to give trimethylidynecyanines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1484–1489, November, 1976.