Reactions of β-oxo-α,β-bis(alkoxycarbonyl)phosphonium ylides based on P-heterocycles

Keglevich, György; Forintos, Henrietta; Ujvári, Anikó; Imre, Tı́mea; Ludányi, Krisztina; Nagy, Z.; Tőke, Lásʐló

doi:10.3184/0308234041423637

Cited by 21 publications

(10 citation statements)

References 8 publications

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“…The phosphorus ylides represent an outstanding achievement of the chemistry of the twentieth century [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. The development of the modern chemistry of natural and physiologically active compounds would have been impossible without the phosphorus ylides [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16].…”

Section: Introductionmentioning

confidence: 99%

“…The development of the modern chemistry of natural and physiologically active compounds would have been impossible without the phosphorus ylides [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. They have found use in a wide variety of reactions of interest to synthetic chemists [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Phosphorus ylides are important reagents in synthetic organic chemistry [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16], especially in the synthesis of naturally occurring products, compounds with biological and pharmacological activity [6].…”

Section: Introductionmentioning

confidence: 99%

“…They have found use in a wide variety of reactions of interest to synthetic chemists [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Phosphorus ylides are important reagents in synthetic organic chemistry [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16], especially in the synthesis of naturally occurring products, compounds with biological and pharmacological activity [6]. These compounds have attained great significance as widely used reagents for linking synthetic building blocks with the formation of carbon-carbon double bonds, and this has aroused much interest in the study of the synthesis, structure and properties of P-ylides and their derivatives [1][2][3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

“…These ylides are most often prepared by the treatment of a phosphonium salt with a base. Most of the phosphonium salts are usually made from phosphine and an alkyl halide [10][11][12][13][14][15][16], and they are also obtained by the Michael addition of phosphorus nucleophiles to activated olefins [10][11][12][13][14][15][16]. β-Additions of nucleophiles to the vinyl group of vinylic phosphonium salts leading to the formation of new alkylidenephosphoranes has attracted much attention as a very convenient and synthetically useful method in organic synthesis [18][19][20][21][22][23][24][25][26][27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

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<b>Vinyltriphenylphosphonium salt-mediated preparation of thiophene-containing electron-poor alkenes from acetylenic esters, 2-thienylmethanol and triphenylphosphine</b>

Shajari

Ramazani

Ahmadi

2011

Bull. Chem. Soc. Eth.

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ABSTRACT ABSTRACT. Protonation of the highly reactive 1:1 intermediates, produced in the reaction between triphenylphosphine and alkyl acetylenecarboxylates (methyl acetylenecarboxylate, ethyl acetylenecarboxylate and ethyl phenylacetylenecarboxylate) by 2-thienylmethanol leads to vinyltriphenylphosphonium salts, which undergo an addition-elimination reaction in CH2Cl2 at room temperature to produce the corresponding O-vinylated alkenes via thiophene-containing phosphorus ylides intermediates in fairly high yields. The structural analysis of all products indicated that the reactions are regio-and stereoselective. KEY WORDS KEY WORDS KEY WORDS

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

<b>Vinyltriphenylphosphonium salt-mediated preparation of thiophene-containing electron-poor alkenes from acetylenic esters, 2-thienylmethanol and triphenylphosphine</b>

Shajari

Ramazani

Ahmadi

2011

Bull. Chem. Soc. Eth.

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“…4 Reactivity of the b-oxophosphoranes 2 was in accord with the structure established by spectroscopy. 5 Depending on the substituents, the transformation requires heating at 150°C for 7-14 days. An additional problem is the inevitable polymerization of DAAD that makes the reaction less efficient and complicates the work-up.…”

mentioning

confidence: 99%

Efficient Synthesis of Cyclic β-Oxophosphoranes by Microwave-Assisted Reaction of Cyclic Phosphine Oxides and Dialkyl Acetylenedicarboxylates

et al. 2006

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The inverse Wittig-type reaction of a series of 2,4,6-trialkylphenyl cyclic phosphine oxides 3, 5, 7, 9, 11, 13, 15, 18 and 20 and dialkyl acetylenedicarboxylate giving b-oxophosphoranes 4, 6, 8, 10, 12, 14, 16, 19 and 21, respectively, can be accomplished in a convenient way under microwave conditions. At 150°C, the MWassisted reaction is more efficient and becomes 50-fold faster as compared to the thermal transformation. A further advantage is that the 2,5-dihydrophosphole moiety of the 2,4,6-triisopropylphenyl derivative 3 does not undergo double-bond rearrangement and that the 2,4,6-trimethylphenyl substrates 11 and 13, otherwise inactive in the reaction under discussion, could also be converted to b-oxophosphoranes 12 and 14. A series of new products 4Bb, 12, 14, 16b, 19 and 21 have been made available.A novel reaction has been discovered by us, in which the interaction of 1-(2,4,6-trialkylphenyl)cyclic phosphine oxides 1 and dialkyl acetylenedicarboxylates (DAAD) react to form the corresponding b-oxophosphoranes 2 that can be regarded to be stabilized phosphonium ylides (Scheme 1). 1-3 As the reaction of the P=O group and the triple bond forms a P=C and a C=O bond, the novel transformation can be regarded to be an inverse Wittig-type reaction. 4 Reactivity of the b-oxophosphoranes 2 was in accord with the structure established by spectroscopy. 5 Depending on the substituents, the transformation requires heating at 150°C for 7-14 days. An additional problem is the inevitable polymerization of DAAD that makes the reaction less efficient and complicates the work-up.In this paper we describe an efficient accomplishment of the P=O + -C≡C-reaction under microwave conditions.Other advantages of the microwave synthesis are also discussed and the reactions extended to new model compounds.We found that the reaction time of the 1 → 2 conversion at 150°C decreased dramatically under microwave conditions. In contrast to the 7-14 days required for the completion applying traditional heating, the microwave-assisted reaction was complete after three to six hours of irradiation. This means an average 50-fold rate acceleration. Moreover, polymerization of the DAAD was suppressed increasing the efficiency and facilitating the purification.Reaction of the 1-(2,4,6-triisopropylphenyl)-2,5-dihydro-1H-phosphole oxide 3 with dimethyl acetylenedicarboxylate (DMAD) was studied in detail (Table 1). It was surprising that in contrast to the result of the thermolysis at 150°C for eight days, 2 the rearrangement of the double bond in the product 4a was only partial. Hence, b-oxophosphorane 4Ba predominated over 4Aa. It was more appropriate to use the components 3 and DMAD as neat, in the absence of toluene. An increase of the excess of DMAD decreased the reaction time and the extent of double bond rearrangement. The use of three to five equivalents of DMAD is the optimum. In a closed system (under 2-3 bar pressure), the reaction is somewhat faster than in an open vessel, the extent of the isomerization is, however, more considerable. Fr...

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Phosphorus Ylides and Related Compounds

2019

Organophosphorus Chemistry

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Reactions of β-oxo-α,β-bis(alkoxycarbonyl)phosphonium ylides based on P-heterocycles

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 21 publications

References 8 publications

<b>Vinyltriphenylphosphonium salt-mediated preparation of thiophene-containing electron-poor alkenes from acetylenic esters, 2-thienylmethanol and triphenylphosphine</b>

<b>Vinyltriphenylphosphonium salt-mediated preparation of thiophene-containing electron-poor alkenes from acetylenic esters, 2-thienylmethanol and triphenylphosphine</b>

Efficient Synthesis of Cyclic β-Oxophosphoranes by Microwave-Assisted Reaction of Cyclic Phosphine Oxides and Dialkyl Acetylenedicarboxylates

Phosphorus Ylides and Related Compounds

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