(6Z,9Z,28Z,31Z)-heptatriaconta-6,9,28,31-tetraen-19-one

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of dilinoleyl ketone (I, previously prepared as described in Example 1, 527 mg, 1.0 mmol), 1,3,4-butanetriol (technical grade, ca. 90%, 236 mg, 2 mmol) and pyridinium p-toluenesulfonate (50 mg, 0.2 mmol) in 50 mL of toluene was refluxed under nitrogen overnight with a Dean-Stark tube to remove water. The resulting mixture was cooled to room temperature. The organic phase was washed with water (2×30 mL), brine (50 mL), and dried over anhydrous Na2SO4. Evaporation of the solvent resulted in a yellowish oily residual (0.6 g). The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with dichloromethane as eluent. This afforded 0.5 g of pure II as colourless oil. 1H NMR (400 MHz, CDCl3) δ: 5.25-5.48 (8H, m, 4×CH═CH), 4.18-4.22 (1H, m, OCH), 4.08 (1H, dd, OCH), 3.82 (2H, t, OCH2), 3.53 (1H, t, OCH), 2.78 (4H, t, 2×C═C—CH2—C═C), 2.06 (8H, q, 4× allylic CH2), 1.77-1.93 (2H, m, CH2), 1.52-1.68 (4H, m, 2×CH2), 1.22-1.45 (32H, m), 0.86-0.94 (6H, t, 2×CH3) ppm. previously prepared was refluxed under nitrogen overnight with a Dean-Stark tube to remove water The organic phase was washed with water (2×30 mL), brine (50 mL) dried over anhydrous Na2SO4 Evaporation of the solvent resulted in a yellowish oily residual (0.6 g) The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with dichloromethane as eluent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of dilinoleyl methanol (2.0 g, 3.8 mmol) and anhydrous sodium carbonate (0.2 g) in 100 mL of CH2Cl2 was added pydimium chlorochromate (PCC, 2.0 g, 9.5 mmol). The resulting suspension was stirred at room temperature for 60 min. Ether (300 mL) was then added into the mixture, and the resulting brown suspension was filtered through a pad of silica gel (300 mL). The silica gel pad was further washed with ether (3×200 mL). The ether filtrate and washes were combined. Evaporation of the solvent gave 3.0 g of an oily residual as a crude product. The crude product was purified by column chromatography on silica gel (230-400 mesh, 250 mL) eluted with 0-3% ether in hexanes. This gave 1.8 g (90%) of dilinoleyl ketone (V). 1H NMR (400 MHz, CDCl3) δ: 5.25-5.45 (8H, m, 4×CH═CH), 2.78 (4H, t, 2×C═C—CH2—C═C), 2.39 (4H, t, 2×COCH2), 2.05 (8H, q, 4× allylic CH2), 1.45-1.7 (4H, m), 1.2-1.45 (32H, m), 0.90 (6H, t, 2×CH3) ppm. the resulting brown suspension was filtered through a pad of silica gel (300 mL) The silica gel pad was further washed with ether (3×200 mL) Evaporation of the solvent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of dilinoleyl methanol (2.0 g, 3.8 mmol) and anhydrous sodium carbonate (0.2 g) in 100 mL of CH2Cl2 was added pydimium chlorochromate (PCC, 2.0 g, 9.5 mmol). The resulting suspension was stirred at room temperature for 60 min. Ether (300 mL) was then added into the mixture, and the resulting brown suspension was filtered through a pad of silica gel (300 mL). The silica gel pad was further washed with ether (3×200 mL). The ether filtrate and washes were combined. Evaporation of the solvent gave 3.0 g of an oily residual as a crude product. The crude product was purified by column chromatography on silica gel (230-400 mesh, 250 mL) eluted with 0-3% ether in hexanes. This gave 1.8 g (90%) of dilinoleyl ketone (V). 1H NMR (400 MHz, CDCl3) δ: 5.25-5.45 (8H, m, 4×CH═CH), 2.78 (4H, t, 2×C═C—CH2—C═C), 2.39 (4H, t, 2×COCH2), 2.05 (8H, q, 4× allylic CH2), 1.45-1.7 (4H, m), 1.2-1.45 (32H, m), 0.90 (6H, t, 2×CH3) ppm. the resulting brown suspension was filtered through a pad of silica gel (300 mL) The silica gel pad was further washed with ether (3×200 mL) Evaporation of the solvent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of dilinoleyl methanol (4.0 g, 7.2 mmol) and anhydrous potassium carbonate (0.4 g) in 100 mL of CH2Cl2 was added pyridinium chlorochromate (PCC, 4.0 g, 19 mmol). The resulting suspension was stirred at room temperature for 2 hours. Ether (300 mL) was then added into the mixture, and the resulting brown suspension was filtered through a pad of silica gel (150 mL). The silica gel pad was further washed with ether (3×75 mL). The ether filtrate and washes were combined. Evaporation of the solvent gave 5.1 g of an oily residual as a crude product. The crude product was purified by column chromatography on silica gel (230-400 mesh, 200 mL) eluted with 0-4% ethyl acetate in hexanes. This afforded 3.0 g (79%) of dilinoleyl ketone (V). the resulting brown suspension was filtered through a pad of silica gel (150 mL) The silica gel pad was further washed with ether (3×75 mL) Evaporation of the solvent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of dilinoleyl methanol (4.0 g, 7.2 mmol) and anhydrous potassium carbonate (0.4 g) in 100 mL of CH2Cl2 was added pyridinium chlorochromate (PCC, 4.0 g, 19 mmol). The resulting suspension was stirred at room temperature for 2 hours. Ether (300 mL) was then added into the mixture, and the resulting brown suspension was filtered through a pad of silica gel (150 mL). The silica gel pad was further washed with ether (3×75 mL). The ether filtrate and washes were combined. Evaporation of the solvent gave 5.1 g of an oily residual as a crude product. The crude product was purified by column chromatography on silica gel (230-400 mesh, 200 mL) eluted with 0-4% ethyl acetate in hexanes. This afforded 3.0 g (79%) of dilinoleyl ketone (V). the resulting brown suspension was filtered through a pad of silica gel (150 mL) The silica gel pad was further washed with ether (3×75 mL) Evaporation of the solvent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of dilinoleyl methanol (4.0 g, 7.2 mmol) and anhydrous potassium carbonate (0.4 g) in 100 mL of CH2Cl2 was added pyridinium chlorochromate (PCC, 4.0 g, 19 mmol). The resulting suspension was stirred at room temperature for 2 hours. Ether (300 mL) was then added into the mixture, and the resulting brown suspension was filtered through a pad of silica gel (150 mL). The silica gel pad was further washed with ether (3×75 mL). The ether filtrate and washes were combined. Evaporation of the solvent gave 5.1 g of an oily residual as a crude product. The crude product was purified by column chromatography on silica gel (230-400 mesh, 200 mL) eluted with 0-4% ethyl acetate in hexanes. This afforded 3.0 g (79%) of dilinoleyl ketone (V). the resulting brown suspension was filtered through a pad of silica gel (150 mL) The silica gel pad was further washed with ether (3×75 mL) Evaporation of the solvent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of dilinoleyl ketone (I, previously prepared as described in Example 1, 1.05 g, 2.0 mmol), 1,2,6-hexanetriol (0.54 g, 4 mmol) and pyridinium p-toluenesulfonate (100 mg, 0.4 mmol) in 150 mL of toluene was refluxed under nitrogen overnight with a Dean-Stark tube to remove water. The resulting mixture was cooled to room temperature. The organic phase was washed with water (2×60 mL), brine (60 mL), and dried over anhydrous Na2SO4. Evaporation of the solvent resulted in a yellowish oily residual (1.5 g). The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with 0-0.5% methanol in dichloromethane as eluent. This afforded 1.4 g of pure II as colourless oil. previously prepared was refluxed under nitrogen overnight with a Dean-Stark tube to remove water The organic phase was washed with water (2×60 mL), brine (60 mL) dried over anhydrous Na2SO4 Evaporation of the solvent resulted in a yellowish oily residual (1.5 g) The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with 0-0.5% methanol in dichloromethane as eluent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of dilinoleyl ketone (I, previously prepared as described in Example 1, 1.05 g, 2.0 mmol), 1,2,6-hexanetriol (0.54 g, 4 mmol) and pyridinium p-toluenesulfonate (100 mg, 0.4 mmol) in 150 mL of toluene was refluxed under nitrogen overnight with a Dean-Stark tube to remove water. The resulting mixture was cooled to room temperature. The organic phase was washed with water (2×60 mL), brine (60 mL), and dried over anhydrous Na2SO4. Evaporation of the solvent resulted in a yellowish oily residual (1.5 g). The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with 0-0.5% methanol in dichloromethane as eluent. This afforded 1.4 g of pure II as colourless oil. previously prepared was refluxed under nitrogen overnight with a Dean-Stark tube to remove water The organic phase was washed with water (2×60 mL), brine (60 mL) dried over anhydrous Na2SO4 Evaporation of the solvent resulted in a yellowish oily residual (1.5 g) The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with 0-0.5% methanol in dichloromethane as eluent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of dilinoleyl ketone (I, previously prepared as described in Example 1, 1.0 g, 2 mmol), 1,2,5-pentanetriol (crude, 0.25 g, 2 mmol) and pyridinium p-toluenesulfonate (100 mg, 0.4 mmol) in 150 mL of toluene was refluxed under nitrogen overnight with a Dean-Stark tube to remove water. The resulting mixture was cooled to room temperature. The organic phase was washed with water (3×40 mL), brine (50 mL), and dried over anhydrous Na2SO4. Evaporation of the solvent gave a yellowish oily residual (1.1 g). The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with 0-1% methanol in dichloromethane as eluent. This afforded 0.90 g of pure II as colourless oil. previously prepared was refluxed under nitrogen overnight with a Dean-Stark tube to remove water The organic phase was washed with water (3×40 mL), brine (50 mL) dried over anhydrous Na2SO4 Evaporation of the solvent gave a yellowish oily residual (1.1 g) The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with 0-1% methanol in dichloromethane as eluent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of dilinoleyl ketone (I, previously prepared as described in Example 1, 1.0 g, 2 mmol), 1,2,5-pentanetriol (crude, 0.25 g, 2 mmol) and pyridinium p-toluenesulfonate (100 mg, 0.4 mmol) in 150 mL of toluene was refluxed under nitrogen overnight with a Dean-Stark tube to remove water. The resulting mixture was cooled to room temperature. The organic phase was washed with water (3×40 mL), brine (50 mL), and dried over anhydrous Na2SO4. Evaporation of the solvent gave a yellowish oily residual (1.1 g). The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with 0-1% methanol in dichloromethane as eluent. This afforded 0.90 g of pure II as colourless oil. previously prepared was refluxed under nitrogen overnight with a Dean-Stark tube to remove water The organic phase was washed with water (3×40 mL), brine (50 mL) dried over anhydrous Na2SO4 Evaporation of the solvent gave a yellowish oily residual (1.1 g) The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with 0-1% methanol in dichloromethane as eluent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of dilinoleyl ketone (I, previously prepared as described in Example 1, 527 mg, 1.0 mmol), 1,3,4-butanetriol (technical grade, ca. 90%, 236 mg, 2 mmol) and pyridinium p-toluenesulfonate (50 mg, 0.2 mmol) in 50 mL of toluene was refluxed under nitrogen overnight with a Dean-Stark tube to remove water. The resulting mixture was cooled to room temperature. The organic phase was washed with water (2×30 mL), brine (50 mL), and dried over anhydrous Na2SO4. Evaporation of the solvent resulted in a yellowish oily residual (0.6 g). The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with dichloromethane as eluent. This afforded 0.5 g of pure II as colourless oil. 1H NMR (400 MHz, CDCl3) δ: 5.25-5.48 (8H, m, 4×CH═CH), 4.18-4.22 (1H, m, OCH), 4.08 (1H, dd, OCH), 3.82 (2H, t, OCH2), 3.53 (1H, t, OCH), 2.78 (4H, t, 2×C═C—CH2—C═C), 2.06 (8H, q, 4×allylic CH2), 1.77-1.93 (2H, m, CH2), 1.52-1.68 (4H, m, 2×CH2), 1.22-1.45 (32H, m), 0.86-0.94 (6H, t, 2×CH3) ppm. previously prepared was refluxed under nitrogen overnight with a Dean-Stark tube to remove water The organic phase was washed with water (2×30 mL), brine (50 mL) dried over anhydrous Na2SO4 Evaporation of the solvent resulted in a yellowish oily residual (0.6 g) The crude product was purified by column chromatography on silica gel (230-400 mesh, 100 mL) with dichloromethane as eluent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of dilinoleyl methanol (2.0 g, 3.8 mmol) and anhydrous sodium carbonate (0.2 g) in 100 mL of CH2Cl2 was added pydimium chlorochromate (PCC, 2.0 g, 9.5 mmol). The resulting suspension was stirred at room temperature for 60 min. Ether (300 mL) was then added into the mixture, and the resulting brown suspension was filtered through a pad of silica gel (300 mL). The silica gel pad was further washed with ether (3×200 mL). The ether filtrate and washes were combined. Evaporation of the solvent gave 3.0 g of an oily residual as a crude product. The crude product was purified by column chromatography on silica gel (230-400 mesh, 250 mL) eluted with 0-3% ether in hexanes. This gave 1.8 g (90%) of dilinoleyl ketone (V). 1H NMR (400 MHz, CDCl3) δ: 5.25-5.45 (8H, m, 4×CH═CH), 2.78 (4H, t, 2×C═C—CH2-C═C), 2.39 (4H, t, 2×COCH2), 2.05 (8H, q, 4×allylic CH2), 1.45-1.7 (4H, m), 1.2-1.45 (32H, m), 0.90 (6H, t, 2×CH3) ppm. the resulting brown suspension was filtered through a pad of silica gel (300 mL) The silica gel pad was further washed with ether (3×200 mL) Evaporation of the solvent