- PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE AMINE DERIVATIVE
-
Optically active amine derivatives are produced by acting on imine derivatives with a culture of microorganisms having the ability to stereoselectively reduce the compounds, microbial cells, or processed products thereof, followed by collecting the generated optically active amine derivatives. Optically active amine derivatives obtained in the present invention are useful as materials for pharmaceutical agents. The present invention enables, for example, production of an optically active compound represented by formula (IV): (wherein R group represents an alkyl group having one to three carbon atoms; and n represents an integer of 1 to 4).
- -
-
-
- PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE AMINE DERIVATIVE
-
Novel enzymes that stereoselectively reduce imine derivatives were isolated and purified, and polynucleotides encoding the enzymes were cloned. Optically active amine derivatives were produced by acting on imine derivatives with a culture of microorganisms having the ability to stereoselectively reduce the compounds, microbial cells or processed products thereof, and/or imine reductases thereof, followed by collecting the generated optically active amine derivatives. The present invention enables, for example, production of an optically active compound represented by formula (IV): (wherein R group represents an alkyl group having one to three carbon atoms; and n represents an integer of 1 to 4).
- -
-
-
- Intramolecular hydroamination of aminoalkynes with silver-phenanthroline catalysts
-
(Chemical Equation Presented) Intramolecular hydroamination of several aminoalkynes catalyzed by silver-phenanthroline complexes is reported. This catalyst system complements previous protocols by employing air- and moisture-stable complexes without compromising activity or reaction control. Some of the hydroamination products are subject to a useful aerobic oxidation. Silver-phenanthroline complexes have successfully demonstrated efficacy in the desymmetrization of a prochiral diyne.
- Carney, Jeffrey M.,Donoghue, Patrick J.,Wuest, William M.,Wiest, Olaf,Helquist, Paul
-
supporting information; experimental part
p. 3903 - 3906
(2009/07/09)
-
- Constrained geometry organoactinides as versatile catalysts for the intramolecular hydroamination/cyclization of primary and secondary amines having diverse tethered C-C unsaturation
-
A series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)2 (CGC = Me2-Si(η5-Me 4C5)(tBuN); An = Th, 1; U, 2), has been prepared via efficient in situ, two-step protodeamination routes in good yields and high purity. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dichlorides (1-Cl2, 2-Cl2) and slightly more soluble diiodides (1-I2, 2-I2) with excess Me3Si-X (X = Cl, I) in non-coordinating solvents. The new complexes were characterized by NMR spectroscopy, elemental analysis, and (for 1 and 2) single-crystal X-ray diffraction, revealing substantially increased metal coordinative unsaturation vs the corresponding Me2SiCp″ 2AnR2 (Cp″ = η5-Me4C 5; An = Th, R = CH2-(SiMe3), 3; An = U, R = CH2Ph, 4) and Cp′2AnR2 (Cp′ = η5-Me5C5 ; An = Th, R = CH 2(SiMe3), 5; An = U, R = CH2(SiMe3), 6) complexes. Complexes 1-6 exhibit broad applicability for the intramolecular hydroamination of diverse C-C unsaturations, including terminal and internal aminoalkenes (primary and secondary amines), aminoalkynes (primary and secondary amines), aminoallenes, and aminodienes. Large turnover frequencies (N t up to 3000 h-1) and high regioselectivities (≥95%) are observed throughout, along with moderate to high diastereoselectivities (up to 90% trans ring closures). With several noteworthy exceptions, reactivity trends track relative 5f ionic radii and ancillary ligand coordinative unsaturation. Reactivity patterns and activation parameters are consistent with a reaction pathway proceeding via turnover-limiting C=C/C=C insertion into the An-N σ-bond.
- Stubbert, Bryan D.,Marks, Tobin J.
-
p. 4253 - 4271
(2008/02/01)
-
- Mechanistic investigation of intramolecular aminoalkene and aminoalkyne hydroamination/cyclization catalyzed by highly electrophilic, tetravalent constrained geometry 4d and 5f complexes. Evidence for an M-N σ-bonded insertive pathway
-
A mechanistic study of intramolecular hydroamination/cyclization catalyzed by tetravalent organoactinide and organozirconium complexes is presented. A series of selectively substituted constrained geometry complexes, (CGC)M(NR 2)Cl (CGC = [Mes
- Stubbert, Bryan D.,Marks, Tobin J.
-
p. 6149 - 6167
(2008/02/04)
-
- A general method for the synthesis of the most powerful naturally?occurring Maillard flavors
-
The natural flavors 2-acetyl-1-pyrroline 1a, 2-propionyl-1-pyrroline 1b, 2-acetyl-3,4,5,6-tetrahydropyridine 1c, 2-acetyl-2-thiazoline 1d, 2-propionyl-2-thiazoline 1e, and the artificial flavor 2-acetyl-5,6-dihydro-4H-1,3-thiazine 1f have been prepared by catalytic SeO2 oxidation of the corresponding cyclic imines 6a-c and sulfur cyclic imines 7a-c using TBHP as co-oxidant. The oxidation of the pyrrolines 1a and b is completely regioselective. Professional olfactory evaluation together with the odor threshold of the new flavor 1f is reported.
- Fuganti, Claudio,Gatti, Francesco G.,Serra, Stefano
-
p. 4762 - 4767
(2007/10/03)
-
- Intramolecular cyclization of aminoalkynes catalyzed by PdMo 3S4 cubane clusters
-
PdMo3S4 cubane clusters [(Cp*Mo) 3(μ3-S)4Pd(L)][PF6] (Cp* = η5-C5Me5; L = dba (2), ma (3); dba = dibenzylideneacetone, ma = maleic anhydride) showed high catalytic activity for the intramolecular hydroamination of aminoalkynes to afford the corresponding cyclic imines in good yields under mild conditions. A molecular structure of 3 has been determined by X-ray diffraction study. Copyright
- Takei, Izuru,Enta, Yutaka,Wakebe, Youhei,Suzuki, Toshiaki,Hidai, Masanobu
-
p. 590 - 591
(2007/10/03)
-
- 4-Pyridyl-and 2,4-pyrimidinyl-substituted pyrrole derivatives and their use in pharmacy
-
The present invention relates to 4-pyridyl- und 2,4-pyrimidinyl-substituted pyrrole derivatives and their use in pharmacy, of the formula 1 in which the variables have the meanings indicated in the description. The compounds according to the invention have immunomodulating and/or cytokine release-inhibiting action and are therefore utilizable for the treatment of disorders which are connected with a disturbance of the immune system.
- -
-
-
- FUSED PYRROLE COMPOUNDS, PHARMACEUTICAL AGENTS CONTAINING THE SAME, AND THE USE THEREOF
-
The present invention relates to fused pyrrole compounds of the formula 1. in which at least one of the radicals R1, R2, R3 is 4-sulphur-substituted phenyl. These compounds are in particular pyrrolizines, indolizines and heteroanalogues having selective inhibitory action on isoenzyme-2 of prostaglandin H synthase (COX-2). The invention also relates to pharmaceutical compositions which contain these compounds; and the use of these compounds for the treatment of disorders of the rheumatic type.
- -
-
-
- Ruthenium-catalyzed intramolecular hydroamination of aminoalkynes
-
Low-valent ruthenium complexes with a π-acidic ligand, such as Ru(η6-cot)(dmfm)2 [cot=1,3,5-cyclooctatriene, dmfm=dimethyl fumarate] and Ru3(CO)12, showed high catalytic activity for the intramolecular hydroamination of aminoalkynes. The reaction is highly regioselective, in which a nitrogen atom is selectively attached to an internal carbon of alkynes to give five-, six-, and seven-membered nitrogen heterocycles as well as indoles in good to high yields.
- Kondo, Teruyuki,Okada, Takumi,Suzuki, Toshiaki,Mitsudo, Take-Aki
-
p. 149 - 154
(2007/10/03)
-
- Synthesis of 2-acyl-3-chloropyrroles: Application to the synthesis of the trail pheromone of the ant Atta texana
-
Alkyl 3-chloropyrrole-2-carboxylates and 2-alkanoyl-3-chloropyrroles are conveniently prepared from 2-alkyl-1-pyrrolines by tetra- and pentahalogenation with N-chlorosuccinimide, subsequent base-induced aromatisation with sodium alkoxides in the corresponding alcohol and final acid hydrolysis of the resulting orthoester or acetal functions into the 3- chloropyrrole. The developed strategy is applied to the synthesis of the trail pheromone of the ant Atta texana.
- Tehrani, Kourosch Abbaspour,Borremans, Didier,De Kimpe, Norbert
-
p. 4133 - 4152
(2007/10/03)
-
- Organolanthanide-catalyzed intramolecular hydroamination/cyclization of aminoalkynes
-
This contribution reports the efficient and regiospecific Cp'2LnCH(SiMe3)2 (Ln = La, Nd, Sm, Lu; Cp' = η5-Me5C5)- and Me2SiCp''2LnCH(SiMe3)2 (Ln = Nd, Sm; Cp'' = η5-Me4C5)-catalyzed hydroamination/cyclization of aliphatic and aromatic aminoalkynes of the formula RC≡C(CH2)(n)NH2 to yield the corresponding cyclic imines RCH2C=N(CH2)(n-1)CH2, where R, n, N(t) h-1 (°C) = Ph, 3, 77 (21°C); Ph, 3, 2830 (60°C); Me, 3, 96 (21°C); CH2=CMeCH2, 3, 20 (21°C); H, 3, 580 (21°C); Ph, 4, 4 (21°C); Ph, 4, 328 (60°C); Ph, 5, 0.11 (60°C); and SiMe3, 3, >7600 (21°C), and of aliphatic secondary amino-alkynes of the formula RC≡C(CH2)3NHR1 to generate the corresponding cyclic enamines RCH=CNR1(CH2)2CH2 where R, R1, N(t) h-1 (°C) = SiMe3, CH2=CHCH2, 56 (21°C); H, CH2=CHCH2, 27 (21°C); SiMe3, CH2=CH(CH2)3, 129 (21°C); and H, CH2=CH(CH2)3, 47 (21°C). Kinetic and mechanistic evidence is presented arguing that the turnover-limiting step is an intramolecular alkyne insertion into the Ln-N bond followed by rapid protonolysis of the resulting Ln-C bond. The use of larger metal ionic radius Cp'2LnCH(SiMe3)2 and more open Me2SiCp''2LnCH(SiMe3)2 complexes as the precatalysts results in a decrease in the rate of hydroamination/cyclization, arguing that the steric demands in the -C≡C- insertive transition state are relaxed compared to those of the analogous aminoolefin hydroamination/cyclization.
- Li,Marks
-
p. 9295 - 9306
(2007/10/03)
-
- A Convenient Synthesis of 2-Methyl/ethyl-Δ1-pyrrolines
-
2-Methyl/ethyl-Δ1-pyrrolines have been conveniently synthesised from commercially available 2-pyrrolidone.
- Ananthapadmanabhan, S.,Raja, T. K.,Srinivasan, V.,Simon, A.
-
-
- CYCLIC β-ENAMINOESTERS DECARBOXYLATION WITH BORIC ACID : A CONVENIENT SYNTHESIS OF CYCLIC IMINES
-
Δ1-pyrrolines, Δ1-piperideines and 1-aza 1-cycloheptenes are formed in good yields from the decarboxylation of alkylated cyclic β-enaminoesters with boric acid.
- Bacos, Daniel,Celerier, Jean-Pierre,Lhommet, Gerard
-
p. 2353 - 2354
(2007/10/02)
-
- Palladium-Catalyzed Oxidation of Amino Alkenes to Cyclic Imines or Enamines and Amino Ketones
-
Amino alkenes of the type CH2=CH(CH2)nNH2 (n = 3,4) are cyclized to pyrrolines or piperideines under ''Wacker process''conditions.Amino alkenes with a secondary amino group yield the corresponding cyclic enamines, while tertiary amino alkenes give amino ketones.
- Pugin, B.,Venanzi, L. M.
-
p. 6877 - 6881
(2007/10/02)
-