ChemInform Abstract: Catalytic Interaction of 1,3‐Diheteracycloalkanes with Diazo Compounds

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

doi:10.1002/chin.200936263

Cited by 2 publications

(2 citation statements)

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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: 86%

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: 86%

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

Раскильдина¹,

Zlotsky²,

Sultanova³

2018

MHC

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“…Abstract-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 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.…”

mentioning

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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ChemInform Abstract: Catalytic Interaction of 1,3‐Diheteracycloalkanes with Diazo Compounds

Cited by 2 publications

References 1 publication

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

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

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

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