Catalytic reaction of 1-chloropropenyl butyl ethers with methyl diazoacetate

Catalytic reaction of trans- and cis-1-chloropropenyl butyl ethers with methyl diazoacetate catalyzed by either Rh₂(OAc)₃, or Cu(OTf)₂, or Cu(acac)₂ in the presence of the imidazolium salts [bmim]⁺ Cl^?, [bmim]⁺ BF ₄ ^? , and [bmim]⁺ PF ₆ ^? was studied. The composition and ratio of products formed was shown to depend on the reaction conditions and the nature and ratio of the components of the catalytic system.     

Catalytic reaction of monosubstituted furazanes with methyl diazoacetate

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, p. 2876, December, 1989.     

Catalytic reaction of methyl diazoacetate with silylated enynes

Factors affecting the regioselectivity of the catalytic reaction of methyl diatoacetate with 1-trimethylsilylalkene-1-ynes have been revealed. Conditions for selective cyclopropanation of the double bond in 1-trimethylsilylbut-3-ene-1-yne and 1-trimethylsilyl-3-methylbut-3-ene-1-yne in the presence of Rh₂(OAc)₄ have been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1248–1252, July, 1993.The authors express their gratitude to B. I. Ugrak and D. E. Dmitriev for help in recording and interpreting the NMR spectra, E. G. Baskir and V. A. Korolyov for taking the chromato-IR spectra and A. A. Kutin for recording the chromato-mass spectra.     

Catalytic cyclopropanation of stereoisomeric 1,3-dichloropropenes with methyl diazoacetate

The catalytic cyclopropanation of cis- and trans-1,3-dichlorpropenes with methyl diazoacetate in the presence of a copper catalyst was studied. The products composition and ratio were shown to depend on the spatial structure of 1,3-dichloropropene.     

The reaction of methyl diazoacetate with 4,4-dimethyl-2-pentyn-1-al and related compounds

Methyl 2-diazo-3-hydroxy-6,6-dimethyl-4-heptynoate was prepared by treating 4,4-dimethyl-2-pentyn-1-al with methyl diazoacetate at room temperature in the absence of catalysts. In the case of related aldehydes, RCCCHO (R = n-Bu, Me₃Si, Et₃Si, Et₃Ge), this unusual reaction is partially or completely suppressed by a competing 1,3-cycloaddition process. The latter leads to a mixture of isomeric 3- and 4-formylpyrazole, one of which cyalodimerizes to form tricyclic hemiaminal.     

Rh2(OAc)4-catalyzed reaction of 1,3-dioxanes with methyl diazoacetate

The reactions of methyl diazoacetate with 1,3-dioxanes in the presence of Rh₂(OAc)₄ afford 1,4-dioxepanes in up to 46% yields. The insertion of methoxycarbonylcarbene into the C—O bond occurs only in the case of 2-phenyl-1,3-dioxanes.     

Demjanov reaction with 1-methyl-2-aminomethylpiperidine

The Demjanov rearrangement with ring expansion proceeds to a slight degree (9%) during the deamination of 1-methyl-2-aminomethylpiperidine with nitrous acid, and the major reaction products are 1-methyl-2-hydroxymethylpiperidine and 6-methylamino-2-hexanone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1654–1658, December, 1970.     

Effect of imidazolium salts on the catalytic reaction of 1,3-dioxolanes with methyl diazoacetate

Effect of imidazolium salts, [bmim]⁺Cl^?, [bmim]⁺BF₄ ^?, and [bmim]⁺PF₆ ^?, on the reaction of 1,3-dioxolanes with methyl diazoacetate in the presence of copper-containing catalysts was studied. The product composition was found to depend on the reaction conditions and the nature and ratio of components of the catalytic system.     

Thermal reaction of allylamines with ethyl diazoacetate

Conclusions Carboethoxycarbene (CEC) generated by the thermolysis of ethyl diazoacetate at 140–175°C reacts with allylamines to give nontrivial amino acids which had been difficult to prepare in good yields.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1680–1682, July, 1985.     

Catalytic aldol-type reaction of aldehydes with ethyl diazoacetate using quarternary ammonium hydroxide as the base

The direct aldol-type condensation of aldehydes with ethyl diazoacetate (EDA) promoted by an organic base and non-metallic catalyst such as tetrabutylammonium hydroxide (TBAOH) gave β-hydroxy-α-diazocarbonyl compounds with moderate to excellent yields. Furthermore, the reactivity and scope of various phase-transfer catalysts as well as electronically divergent aldehydes are discussed.     

Catalytic reaction of methyl formate with amines to formamides

A feasible procedure of using methyl formate as cheap reagent for the conversion of aliphatic and aromatic amines into formamides with high yields is reported. The improved amine formylation method proceeds mainly at room temperature and in presence of bicyclic guanidines as catalysts. A verifiable key intermediate of outstanding formylating activity is generated from methyl formate and the catalyst in the reaction mixture.     

5-Methyl-2-phenyl-2H-1,2,3-diazaarsole in reaction with ethyl diazoacetate

5-Methyl-2-phenyl-2H- 1,2,3-diazaarsole 1 reacts with ethyl diazoacetate to form a 1:1 bicyclic product 3a , 8-ethoxycarbonyl-4-methyl-2-phenyl-1-arsa-2,3,6,7-tetraazabicyclo[3.3.0]octa-3.7-diene. The latter isomerizes to a two-coordinate arsenic compound 5 , 3-ethoxycarbonyl-5-[α-(phenylhydrazono)ethyl] 1-1,2,4-diazaarsole. The X-ray crystal structure analyses of both products 3a and 5 have been carried out.     

Catalytic [2+1]-cycloaddition of ethyl diazoacetate to fullerene [60]

Cyclopropanation of C₆₀-fullerene was performed with ethyl diazoacetate in the presence of Pd(PPh₃)₄ catalyst. A probable reaction mechanism is suggested.     

Conformational analysis of methyl 2-methyl-2-(1-naphthyl)propionate

(S)-2-Methoxy-2-(1-naphthyl)propionic acid (MαNP acid 1) is used for enantioseparation of many secondary alcohols and for determining the stereogenic centers. In the liquid state, based on the ¹H NMR anisotropy effect and reported results, it was shown that the MαNP ester preferred a coplanar relation between the methyl and naphthyl groups and a synperiplanar relation between the Cα-OMe and CO groups. In the case of 1,2,3,4-tetrahydro-4-phenanthrenol, which is a secondary alcohol, the stereogenic center was determined by X-ray analysis. It was shown that MαNP ester adopted similar arrangements in the solid state. However, it was presumed that the strong repulsion between oxygen atoms may be disadvantageous in the solid state. Therefore, we carried out conformational analysis using the simplest MαNP methyl ester to clarify this unique relationship. From detailed results based on the energy surface determined using the RHF/STO-3G basis set, the synperiplanar positional relation was the most stable, and the calculated results agreed with many reported experimental results. At the same time, all conformational isomers of the MαNP methyl ester were used to clarify the internal conversion pathways.     

Direct aldol condensation reaction of ethyl diazoacetate with trifluoromethyl ketones

An efficient and direct aldol-type condensation of ethyl diazoacetate with trifluoromethyl ketones was developed in the presence of dialkyl zinc. A series of trifluoromethylated products were obtained in good to excellent yields (60-95%). A preliminary extension to a catalytic enantioselective aldol reaction of ethyl diazoacetate to trifluoromethyl ketones (up to 72% ee) is also described.     

Diels-alder reaction of 1-methylcycloprop-2-ene-1-carbonitrile with methyl 2-oxo-2H-pyran-5-carboxylate

The Diels-Alder reaction of 1-methylcycloprop-2-ene-1-carbonitrile and coumalic acid methyl ester (methyl 2-oxo-2H-pyran-5-carboxylate) gave a 2:1 adduct with endo-syn configuration of both cyclopropane fragments, which was established by X-ray analysis. According to the ¹H NMR data, the reaction involves intermediate formation of decarboxylated 1:1 adduct having a cycloheptatriene structure; its isomerization into the corresponding caradiene, followed by addition of the second dienophile molecule, was confirmed by quantum-chemical calculations.