Showing papers by "Yasutaka Ishii published in 2000"
TL;DR: Highly efficient catalytic oxidation of alcohols with molecular oxygen by N-hydroxyphthalimide (NHPI) combined with a Co species was developed and 2-octanol in the presence of catalytic amounts of NHPI and Co(OAc)2 under atmospheric dioxygen in AcOEt at 70 degrees C gave 2- Octanol in 93% yield.
Abstract: Highly efficient catalytic oxidation of alcohols with molecular oxygen by N-hydroxyphthalimide (NHPI) combined with a Co species was developed. The oxidation of 2-octanol in the presence of catalytic amounts of NHPI and Co(OAc)2 under atmospheric dioxygen in AcOEt at 70 °C gave 2-octanone in 93% yield. The oxidation was significantly enhanced by adding a small amount of benzoic acid to proceed smoothly even at room temperature. Primary alcohols were oxidized by NHPI in the absence of any metal catalyst to form the corresponding carboxylic acids in good yields. In the oxidation of terminal vic-diols such as 1,2-butanediol, carbon−carbon bond cleavage was induced to give one carbon less carboxylic acids such as propionic acid, while internal vic-diols were selectively oxidized to 1,2-diketones.
196 citations
TL;DR: Iridium complexes were found to promote the conversion of allyl homoallyl ethers to gamma,delta-unsaturated carbonyl compounds and presumably proceeds through double bond migration to allyl vinyl ethers, which then undergo the Claisen rearrangement.
43 citations
TL;DR: In this paper, a reaction of cyclohexanone with very small amounts of Mn(OAc)2 and Co(OAC)2 under air (1 atm) gave 2-octylcyclochenanone in good selectivity, and from styrene, a six-membered cyclic peroxide was isolated in good yield.
43 citations
41 citations
TL;DR: In this paper, the NHPI-catalyzed co-oxidation of 3-methylpyridine and 4-methyl pyridine by Co(OAc)2−Mn(OAC)2 at 150 °C for 1 h was shown to yield 3-pyridinescarboxylic acid (85%).
39 citations
TL;DR: In this paper, a catalytic method for α-hydroxy carbon radical generation from alcohols has been developed and a convenient and sustainable approach to α -hydroxy-γ-lactones has been constructed.
36 citations
TL;DR: In this article, three-component coupling reactions of aliphatic aldehydes, amines and ethyl diazoacetate to the corresponding aziridine derivatives has been achieved by the use of [Ir(cod)Cl]2 as a catalytic catalyst under mild conditions.
35 citations
TL;DR: In this article, a cyclopentene reaction under O 2 (1 atm) in aqueous acetonitrile acidified by CH 3 SO 3 H in the presence of [Pd(OAc) 2 -NPMoV/C] at 50°C was reported.
34 citations
TL;DR: In this paper, a novel catalytic hydroxyacylation of alkenes using 1,3-dioxolanes and molecular oxygen has been developed, and the reaction of 2-methyl-1,3 dioxolane with methyl acrylate under dioxygen atmosphere in the presence of catalytic amounts of NHPI and Co(OAc)2 produced 81% yield.
29 citations
TL;DR: In this paper, Olefins were smoothly epoxidized under O 2 (1 atm) conditions in the presence of a hydrocarbon such as ethylbenzene or tetralin, using N-hydroxyphthalimide (NHPI) and Mo(CO)6 as catalyst.
28 citations
TL;DR: In this article, an efficient method for hydrogen peroxide via aerobic oxidation of alcohols was achieved by the use of N-hydroxyphthalimide (NHPI) as a catalyst.
TL;DR: The acetalization of terminal alkenes such as ethyl acrylate and acrylonitrile with alcohols under O2 was efficiently achieved by Pd(OAc)2 supported on activated carbon combined with molybdovanadophosphate (NPMoV).
TL;DR: In this article, a new method for the synthesis of 1,3-oxazolidine derivatives has been developed, which is based on the reaction of imines with epoxides in the presence of a catalytic amount of a samarium compound.
TL;DR: Meerwein-Ponndorf-Verley type reductive acetylation of carbonyl compounds to acetates was successfully carried out in the presence of isopropenyl acetate under the influence of a catalytic amount of Ln(O i Pr) 3 at room temperature.
TL;DR: In this paper, the treatment of homoallylic alcohols with NaIO 4 /NaHSO 3 reagent in aqueous t-BuOH under mild conditions produced tetrahydrofuran derivatives together with iodohydrins in a stereospecific manner.
TL;DR: Various alpha-trimethylsilyloxydinitriles were synthesized in good yields by allowing oxime esters or acid anhydrides to react with Me(3)SiCN in the presence of a catalytic amount of La(O(i)()Pr)(3).
Abstract: The reaction of oxime esters with cyanotrimethylsilane (Me3SiCN) under the influence of a catalytic amount of lanthanide compounds produced α-trimethylsilyloxydinitrile derivatives in excellent yields accompanied with the formation of trimethylsilyl oxime ethers. Among the lanthanoid catalysts examined, La(OiPr)3 was found to be the best catalyst. The reaction seems to proceed through the formation of acyl cyanides as intermediates, followed by the addition of Me3SiCN to them. Additionally, the reaction of acetic anhydride with Me3SiCN catalyzed by La(OiPr)3 gave 1-trimethylsilyloxyethane dinitrile. Thus, various α-trimethylsilyloxydinitriles were synthesized in good yields by allowing oxime esters or acid anhydrides to react with Me3SiCN in the presence of a catalytic amount of La(OiPr)3.
Patent•
01 Sep 2000
TL;DR: In this paper, a nitrogen-containing heterocyclic compound of the following formula (1): wherein each of R1 and R2 is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an aryl group and a cycloalkyl groups, a hydroxyl group.
Abstract: A catalyst is for use in a reaction using an oxygen-atom-containing reactant and includes a nitrogen-containing heterocyclic compound of the following formula (1): wherein each of R1 and R2 is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, and R1 and R2 may be combined to form a double bond or to form an aromatic or non-aromatic ring with the adjacent two carbon atoms, where one or two of heterocyclic ring containing three nitrogen atoms indicated in the formula may be further formed on the R1 or R2, or on the double bond or aromatic or non-aromatic ring formed by R1 and R2; X is an oxygen atom or a hydroxyl group; and Y is a single bond, a methylene group, or a carbonyl group. This catalyst can introduce an oxygen-atom-containing group into an organic substrate under mild conditions.
TL;DR: In this article, the use of samarium complexes (II), namely SmI2 and Cp*2Sm (thf) 2, as catalysts for organic synthesis has attracted considerable attention.
Abstract: The utilization of lanthanide metal salts and organolanthanide compounds in organic synthesis has been attracted considerable attention, however, there have been a limited number of studies on the synthetic reactions using divalent samarium compounds such as SmI2 and Cp*2Sm (thf) 2 as catalysts or catalyst precursors. We report here several synthetic reactions by the use of samarium complexes (II), namely SmI2 and Cp*2Sm (thf) 2, as catalysts : (i) coupling reaction of vinyl esters with aldehydes, (ii) acylation of alcohols and amines with vinyl esters, (iii) acylation of tertiary alcohols with vinyl esters in the presence of a catalytic amount of oxime ester, (iv) synthesis of 1, 3-diol monoesters by the trimerization of aldehydes, (v) aldol type condensation of imines, and (vi) one-pot synthesis of pyrroles by the reaction of amines, aldehydes, and nitroalkanes.
Patent•
08 Jun 2000
TL;DR: In this paper, the authors proposed a method for efficiently oxidizing a cycloalkane under mild conditions in the absence of a specific reducing agent, or the like, by oxidizing it as a substrate with molecular oxygen in the presence of a certain compound and a cobalt compound, in a molar ratio of the compound C to the compound D of (95:5) to (5:95).
Abstract: PROBLEM TO BE SOLVED: To provide a method for efficiently oxidizing a cycloalkane under mild conditions in the absence of a specific reducing agent, or the like, by oxidizing the cycloalkane as a substrate with molecular oxygen in the presence of a specific compound and a cobalt compound. SOLUTION: This method comprises oxidizing (A) a cycloalkane as a substrate with (B) molecular oxygen in the presence of (C) 0.001-1 mol, pref. around 0.05 to 0.25 mol, per mol of the component A, of an imide compound of the formula [R1 and R2 are each H, a halogen, a (cyclo)alkyl, an aryl, OH, an alkoxy(carboxyl), COOH or an acyl, or bound together to form a double bond or a (non)aromatic ring; X is O or OH; (n) is 1-3] as an oxidation catalyst (e.g. N-hydroxyphthalimide) and (D) a cobalt compound as a cooxidizing agent, in a molar ratio of the compound C to the compound D of (95:5) to (5:95), pref. (85:15) to (50):(50).
TL;DR: In this paper, a new method for the synthesis of 1,3-oxazolidine derivatives has been developed, which is based on the reaction of imines with epoxides in the presence of a catalytic amount of a samarium compound.
Abstract: A new method for the synthesis of 1,3-oxazolidine derivatives has been developed. Thus, a variety of 1,3-oxazolidines was prepared by the reaction of imines with epoxides in the presence of a catalytic amount of a samarium compound such as SmI 2 , SmI 3 , or Cp* 2 Sm(thf) 2 .
Patent•
25 Jan 2000
TL;DR: In this paper, a process for 1,3-oxazolidine derivatives was described, where an imine derivative of the Periodic Table of Elements (table 3 elements) was used as a catalyst.
Abstract: A process produces 1,3-oxazolidine derivatives by
reacting an imine derivative of the following formula (1):
with an epoxy compound of the following formula (2):
to yield an oxazolidine derivative of the following formula
(3):
A compound of Group 3 elements of the Periodic Table of
Elements, or other metallic compounds can be used as a
catalyst. In the formulae, R 1 , R 2 , R 4 , R 5 , R 6 , and R 7 are each,
independently, a hydrogen atom, a hydrocarbon group, or a
heterocyclic group, and R 3 is a hydrogen atom, a hydrocarbon
group, a heterocyclic group, a hydroxyl group, a substituted
oxy group, or an amino group which may have a substituent,
where a combination of R 1 and R 2 , R 4 and R 5 , R 6 and R 7 , or R 4
and R 6 may be combined to form a ring with the adjacent carbon
atom or carbon-carbon bond. The process can easily yield
1,3-oxazolidine derivatives from readily available
materials.
Patent•
02 Mar 2000
TL;DR: In this article, an organic substrate is reacted with sulfur oxide in the presence of a metallic compound catalyst in the absence of N-hydroxy and N-oxo cyclic imide compound to provide the corresponding organic sulfur-acid or the salt thereof.
Abstract: PROBLEM TO BE SOLVED: To provide a method for efficiently producing an organic sulfur-acid or a salt thereof under a mild condition. SOLUTION: An organic substrate is reacted with sulfur oxide in the presence of a metallic compound catalyst in the absence of N-hydroxy and N-oxo cyclic imide compound to provide the corresponding organic sulfur-acid or the salt thereof. (a) A homo- or heterocyclic compound having a methylene group, (b) a compound having a methine carbon atom, (c) a compound having a methyl group or a methylene group at the adjacent position of an unsaturated bond, (d) a nonaromatic heterocyclic compound having a carbon-hydrogen bond at the adjacent position of a heteroatom, (e) a linear alkane and the like are cited as the organic substrate. Sulfur dioxide or the like can be used as the sulfur oxide.
Patent•
01 Sep 2000
TL;DR: In this article, a nitrogen-containing heterocyclic compound of the following formula (1): wherein each of R1 and R2 is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an aryl group and a cycloalkyl groups, a hydroxyl group.
Abstract: A catalyst is for use in a reaction using an oxygen-atom-containing reactant arid includes a nitrogen-containing heterocyclic compound of the following formula (1): wherein each of R1 and R2 is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, and R1 and R2 may be combined to form a double bond or to form an aromatic or non-aromatic ring with the adjacent two carbon atoms, where one or two of heterocyclic ring containing three nitrogen atoms indicated in the formula may be further formed on the R1 or R2, or on the double bond or aromatic or non-aromatic ring formed by R1 and R2; X is an oxygen atom or a hydroxyl group; and Y is a single bond, a methylene group, or a carbonyl group This catalyst can introduce an oxygen-atom-containing group into an organic substrate under mild conditions
Patent•
13 Nov 2000
TL;DR: In this article, a method for producing the lactam, comprising reacting at least one compound selected from the cycloalkane, the cycloencalkanol or the cycloealkanone with ammonia and oxygen in the presence of an imide compound catalyst having an N-hydroxy(or N-oxo)cyclic imide skeleton to obtain the corresponding lactam was proposed.
Abstract: PROBLEM TO BE SOLVED: To provide a method for producing a lactam, by which the corresponding lactam can be produced from a cycloalkane, a cycloalkanol or a cycloalkanote in one step. SOLUTION: This method for producing the lactam, comprising reacting at least one compound selected from the cycloalkane, the cycloalkanol or the cycloalkanone with ammonia and oxygen in the presence of an imide compound catalyst having an N-hydroxy(or N-oxo)cyclic imide skeleton to obtain the corresponding lactam. The imide compound catalyst includes a compound represented by formula (1) (R1 and R2 are each H, a halogen atom, an alkyl, an aryl, a cycloalkyl, or the like, or R1 R2 may be bound to each other to form a double bond, or an aromatic or non-aromatic ring; X is O or HO).
TL;DR: In this paper, the authors showed that 1]-trimethylsilyl)oxy]-1,10-undecadiene involving an enol moiety and a terminal double bond can be selectively oxidized under phase-transfer conditions.
Abstract: Dehomologation of aldehydes has been first successfully achieved via oxidative cleavage of silyl enol ethers, derived from aldehydes and trimethylchlorosilane, using aqueous hydrogen peroxide in the presence of a catalytic amount of peroxotungstophophate (PCWP) under phase-transfer conditions. For instance, the oxidation of 1-[(trimethylsilyl)oxy]-1-octene resulting from octanal and Me3SiCl with 35% H2O2 catalyzed by PCWP in dichloromethane at room temperature afforded the one-carbon shorter aldehyde, heptanal, in 79% yield. A variety of silyl enol ethers were also converted into one-carbon shorter aldehydes in good yields. The oxidation under homogeneous conditions using tert-butyl alcohol gave hydrolysis products such as 2-oxooctanol and octanal. It is of interest that [1-(trimethylsilyl)oxy]-1,10-undecadiene involving an enol moiety and a terminal double bond afforded exclusively 9-decenal, in which the enol moiety was selectively oxidized. A plausible reaction path for the oxidative cleavage of silyl ...