Reaction of methyl diazoacetate with unsaturated heterocyclic derivatives of carbonyl compounds catalyzed by Rh2(OAc)4

Khanova, M. D.; Sultanova, R. M.; Докичев, В. А.; Злотский, С. С.

doi:10.1134/s0012500807050023

Cited by 6 publications

(3 citation statements)

References 8 publications

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“…The attack of methoxycarbonylcarbane formed during the decomposition of methyldiazoacetate in the presence of rhodium catalyst gives intermediate ylide 45, and its further stabilization leads to the products of Stevens rearrangement 46 and [2,3]-sigmatropic rearrangement 47. As it was shown in works [33,34] the selectivity of the process is influenced by both electronic and steric factors of the heterocyclic fragment substituents. …”

Section: Intermolecular Reactionsmentioning

confidence: 84%

Diazo Compounds in the Synthesis of O- and S-Containing Macroheterocycles

Раскильдина¹,

Zlotsky²,

Sultanova³

2018

MHC

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The review summarizes, systematizes and analyzes literature data of the synthesis of oxygen-and sulfur-containing macroheterocyclic systems using Rh and Cu-catalyzed reactions of diazocarbonyl compounds over the last 15-20 years. The review considers the intra-and intermolecular reactions of introduction of diazocarbonyl compounds, which are used in synthesis of practically important biologically active compounds, via the C-O and C-S bonds.Keywords: Carbenoids, α-diazo carbonyl compounds, O,S-macroheterocycles, cyclic acetals, C-O and C-S insertions, catalysis, ylides. Диазосоединения в синтезе О -и S -содержащих макрогетероциклов

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Section: Intermolecular Reactionsmentioning

confidence: 84%

Diazo Compounds in the Synthesis of O- and S-Containing Macroheterocycles

Раскильдина¹,

Zlotsky²,

Sultanova³

2018

MHC

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“…Ethyl diazoacetate (EDA) is a highly welcomed chemical reagent with significance as the precursor of the carbene to synthesize some key intermediates of pesticides. − For instance, EDA can conduct aldol-type condensation with aldehyde or react with ketone to obtain α-diazo-β-hydroxy esters − and can provide α-carbonyl carbenes to undergo O–H or C–H insertion to π-bonds to form ylides; − similar to the report on the polymerization of allyl diazoacetate by Liu et al, the carbene polymerization with α-carbonyl diazo compounds as carbene precursor has attracted much attention recently. , It is noticed that all of these reactions involve the decomposition of EDA to generate carbenes (eq ) and the carbenes could combine various transition metals to form metal carbenes as active catalytic intermediates . Therefore, the kinetics of EDA decomposition has been the main concern.…”

Section: Introductionmentioning

confidence: 93%

Thermal Decomposition of Ethyl Diazoacetate in Microtube Reactor: A Kinetics Study

Xin

2018

ACS Omega

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Ethyl diazoacetate (EDA) commonly experiences intensive decomposition as well as complex conversion concerning safety and efficiency. In this work, a careful kinetics study on the thermal decomposition of EDA was isothermally conducted in a microtube reactor to establish a mechanism-based kinetic model. The model parameters were well calibrated with experimental data including the yield of dimmers and the conversion of EDA, confirming the rationality of the proposed three-step reaction route. It allows the model to concisely describe the complex species transformations during EDA decomposition, which is unavailable for an apparent kinetic model. Considering an isothermal reaction system and the tolerance of EDA consumption by thermal decomposition, this work could help reveal the requirement on the kinetic characteristics of the desired catalytic reaction in which EDA is involved, as a reference on reaction process modeling and regulation.

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“…Catalytic reactions of saturated and 2-alkenyl-substituted 1,3-dioxolanes or their N-, S-heteroanalogs with alkyl diazoacetates are known to afford the 1,4-dioxane, morpholine, and oxathiane derivatives as a result of intramolecular rearrangement of the arising oxonium, ammonium, or sulfonium ylides [1,2]. In the reaction of N 2 CHCO 2 Me with 1,3-dioxanes in the presence of Rh 2 (OAc) 4 1,4-dioxepane derivatives were synthesized in up to 46% yields.…”

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confidence: 99%

Cyclopropanation of 5-(allyloxymethyl)- and 5-(methallyloxymethyl)-5-ethyl-1,3-dioxanes with methyl diazoacetate

et al. 2011

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Reactions of 5-(allyloxymethyl)-and 5-(methallyloxymethyl)-5-ethyl-1,3-dioxanes with methyl diazoacetate catalyzed by Rh 2 (OAc) 4 or Cu(OTf) 2 in the presence of [bmim] + Clˉ, [bmim] + BF 4ˉ, and [bmim] + PF 6ˉ proceed regioselectively at the C=C bond and lead to the formation of the corresponding cyclopropane-containing 1,3-dioxanes in yields up to 62%.Catalytic reactions of saturated and 2-alkenyl-substituted 1,3-dioxolanes or their N-, S-heteroanalogs with alkyl diazoacetates are known to afford the 1,4-dioxane, morpholine, and oxathiane derivatives as a result of intramolecular rearrangement of the arising oxonium, ammonium, or sulfonium ylides [1,2]. In the reaction of N 2 CHCO 2 Me with 1,3-dioxanes in the presence of Rh 2 (OAc) 4 1,4-dioxepane derivatives were synthesized in up to 46% yields. The reaction of methoxycarbonylcarbene at the C-O bond occurs only with 1,3-dioxanes containing a phenyl substituent in the position 2 of the heterocycle [3]. At the same time the reaction of the linear allylacetals with diazocarbonyl compounds in the presence of Cu-or Rh-containing catalysts occurs nonselectively and leads to the formation both of the products of the alkoxycarbonylcarbene insertion into the C-O bond and of the corresponding cyclopropanation products of the double C=C bond [4,5].In this research we studied the reactions of 5-(allyloxymethyl)-and 5-(methallyloxymethyl)-5-ethyl-1,3-dioxanes (Ia, Ib) containing an allyl fragment in the position 5 of the heterocycle with N 2 CHCO 2 Me both in the presence of Rh 2 (OAc) 4 or Cu(OTf) 2 and also at the use of [bmim] + Clˉ, [bmim] + BF 4 , and [bmim] + PF 6 as cocatalysts.It was established that the application of Rh 2 (OAc) 4 or Cu(OTf) 2 in the reaction of 5-(allyloxymethyl)-5-ethyl-1,3-dioxane (Ia) with methyl diazoacetate in CH 2 Cl 2 or ClCH 2 CH 2 Cl at the molar ratio 1,3-dioxane-N 2 CHCO 2 Me-catalyst 1 : 1 : 0.01 was of low effi ciency. Methyl cyclopropanecarboxylate IIa formed in only 5% yield as a mixture of trans-and cis-isomers in the ratio 1 : 1 (Table 1). The addition of 1 mol% of [bmim] + BF 4ˉ results in the increase of the overall yield of ester IIa to 57% and to the change in the isomers ratio (trans-cis 2.5 : 1).

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Reaction of methyl diazoacetate with unsaturated heterocyclic derivatives of carbonyl compounds catalyzed by Rh2(OAc)4

Cited by 6 publications

References 8 publications

Diazo Compounds in the Synthesis of O- and S-Containing Macroheterocycles

Diazo Compounds in the Synthesis of O- and S-Containing Macroheterocycles

Thermal Decomposition of Ethyl Diazoacetate in Microtube Reactor: A Kinetics Study

Cyclopropanation of 5-(allyloxymethyl)- and 5-(methallyloxymethyl)-5-ethyl-1,3-dioxanes with methyl diazoacetate

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