Synthesis of Monosubstituted 1,1-Dicarbonyl Ester 1,3-Dienes

Olivier Rousseau; Thierry Delaunay; Raphaël Robiette

doi:10.1055/s-0033-1340468

Synlett, Table of Contents

Synlett 2014; 25(4): 519-522
DOI: 10.1055/s-0033-1340468

letter

Synthesis of Monosubstituted 1,1-Dicarbonyl Ester 1,3-Dienes

Authors

Olivier Rousseau

Institute of Condensed Matter and Nanosciences, Université catholique de Louvain, Place Louis Pasteur 1, L4.01.02, 1348 Louvain-la-Neuve, Belgium Fax: +32(0)10474168 Email: raphael.robiette@uclouvain.be
Thierry Delaunay

Institute of Condensed Matter and Nanosciences, Université catholique de Louvain, Place Louis Pasteur 1, L4.01.02, 1348 Louvain-la-Neuve, Belgium Fax: +32(0)10474168 Email: raphael.robiette@uclouvain.be
Raphaël Robiette*

Institute of Condensed Matter and Nanosciences, Université catholique de Louvain, Place Louis Pasteur 1, L4.01.02, 1348 Louvain-la-Neuve, Belgium Fax: +32(0)10474168 Email: raphael.robiette@uclouvain.be

Abstract

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Abstract

The synthesis of various electron-deficient 1,1-dicarbonyl ester 1,3-dienes substituted in position 2 or 3 of the diene moiety has been developed.

Keywords

bromine - condensation - cross-coupling - 1,3-dienes - malonates

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References

References and Notes

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21 General procedures are reported below while characterization of all synthesized compounds (dienes and intermediates) is given in the Supporting Information. Synthesis of Dimethyl (2-Methylprop-2-en-1-ylidene)malonate (2a): In a round-bottomed flask was added THF (12 mL), under argon. A solution of TiCl₄ (6 mmol) in CCl₄ (1.5 mL) was then added, slowly, at 0 °C. After 10 min, methacrolein (3 mmol) and dimethyl malonate (1.5 mmol) were added dropwise. The solution was stirred at 0 °C for 20 min. Pyridine (12 mmol) was then added dropwise and the solution was allowed to warm to r.t. After 16 h of stirring, the reaction mixture was diluted with Et₂O (10 mL) and H₂O (10 mL). The phases were separated and the aqueous phase was extracted with Et₂O (2 × 10 mL). The organic phases were combined, washed with a sat. NaHCO₃ solution (10 mL) and then brine (10 mL). The organic layer was dried over Na₂SO₄, filtered and concentrated under reduced pressure. Typical Procedure for the Knoevenagel Condensation Reaction (3 → 4): In a one-necked round-bottomed flask were added malonate (93 mmol) and aldehyde 3 (110 mmol) in absolute EtOH (40 mL). AcOH (17 mmol) and piperidine (13 mmol) were then added dropwise. The solution was heated at reflux for 48 h (110 °C). The by-product was then distilled in a Kugelrohr apparatus under reduced pressure to yield the diene in an excellent yield. Typical Procedure for the Bromination Reaction (4 → 5): In a one-necked round-bottomed flask were added diethyl malonate compound 4 (8 mmol) and bromine (10 mmol) in CCl₄ (8 mL), at 0 °C. The reaction mixture was stirred at this temperature for 1 h and then at r.t. for 4 h. The reaction mixture was diluted with CH₂Cl₂ (10 mL), then washed with a solution of 1 M NaOH (10 mL) and brine (10 mL). The organic layer was dried over MgSO₄, filtered and concentrated under reduced pressure to provide the desired compound in a good yield. Typical Procedure for the Elimination Reaction (5 → 6): In a one-necked round-bottomed flask, under argon atmosphere, was added the dibromo compound 5 (2.4 mmol) in CH₂Cl₂ (20 mL) at 0 °C. DBU (3.5 mmol) was then added slowly and the reaction mixture was stirred at 0 °C for 30 min. It was then diluted with CH₂Cl₂ (20 mL) and H₂O (20 mL). A solution of 1 M HCl (10 mL) was added and the two phases were separated. The organic phase was dried over MgSO₄, filtered and concentrated. The compound was relatively unstable and was therefore engaged immediately in the next step without further purification. Typical Procedure for the Suzuki Reaction (6 → 7): In a one-necked round-bottomed flask, under argon atmosphere, were added the monobromo compound 6 (3.6 mmol), potassium vinyltrifluoro-borate (4.3 mmol) and PdCl₂dppf (0.18 mmol) in a solution of EtOH (20 mL) and Et₃N (5.3 mmol) previously degassed. The reaction mixture was heated at 40 °C for 16 h and then concentrated under vacuum. The residue was diluted with EtOAc (40 mL), washed successively with H₂O (20 mL), a solution of sat. NH₄Cl (20 mL), and brine (20 mL). The organic layer was dried over MgSO₄, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography with a mixture of cyclohexane and EtOAc. Typical Procedure for Michael Addition (4 → 8): CuI (2.8 mmol) was dissolved in THF (20 mL) under inert atmosphere. A 0.583 M solution of vinylmagnesium bromide in THF (10.1 mL, 5.9 mmol) was added dropwise at 0 °C and the reaction mixture was stirred for 45 min at this temperature. A solution of compound 4 (2.3 mmol) in THF (20 mL) was then added dropwise at –78 °C. The reaction mixture was stirred overnight (the cooling bath warming slowly to r.t.). The reaction was quenched with a sat. NH₄Cl solution (5 mL) and diluted with H₂O (10 mL) and Et₂O (50 mL). After layers separation, the aqueous phase was extracted with Et₂O (2 × 30 mL). The combined organic layers were washed with brine, dried over MgSO₄, and finally concentrated under reduced pressure. The residue was purified by flash chromatography (EtOAc–cyclohexane, 10:90) to give the desired product. Typical Procedure for Double Bond Reformation (8 → 7): Compound 8 (1 mmol) was dissolved in DMF (5 mL) under inert atmosphere. NaH (60% dispersion in mineral oil; 1.2 mmol) was then added at 0 °C. The mixture was stirred for 1 h at r.t. (= solution A). In another flask PhSeCl (2 mmol) was dissolved in DMF (5 mL). This solution was cooled to –10 °C, and then added, very slowly (over 2 h) to solution A. This mixture was stirred for two more hours at –10 °C and then for 2 h at 0 °C. H₂O₂ (30% solution in H₂O; 15 mmol) was added at 0 °C and the solution was stirred for 30 min at this temperature. The reaction was quenched with a sat. NaHCO₃ solution (5 mL), diluted with H₂O (20 mL) and extracted with EtOAc (2 × 20 mL). The combined organic layers were washed with H₂O (10 mL), brine (10 mL), dried over MgSO₄, and concentrated under reduced pressure. The residue was purified by flash chromatography (5:95 → 10:90, EtOAc–cyclohexane) to give the desired product.

Supplementary Material

Supporting Information (PDF)