dodec-11-yn-1-ol

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

Procedure: The same procedure for 8-nonyn-1-ol was followed with 9-dodecyn-1-ol (4.68 g, 25.7 mmol), KH(3.09 g, 77.0 mmol), and 1,3-diaminopropane (70 mL). This produced 4.33 g of yellow oil (93%): IR (neat) ν 3317,2930, 2121 cm−1; 1H—NMR δ 3.62 (t, 2H, J=6.6 Hz), 2.17 (td, 2H, J=2.6 Hz, 7.1 Hz), 1.93 (t, 1H, J=2.6 Hz), 1.76 (bs, 1H), 1.55 (m, 4H), 1.28 bm, 12H); 13C—NMR δ 84.8, 68.0, 63.0, 32.7, 29.5, 29.4 (2C), 29.0, 28.7, 28.4, 25.7, 18.4; MS m/z 189.18 (M++Li).

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

Procedure: tert-Butyldiphenylsilyl chloride (TBDPSCl, 8.70 g, 31.65 mmol) was slowly added to a 0° C. solution of dodec-11-yn-1-ol (4.80 g, 26.37 mmol) and imidazole (3.23 g, 47.47 mmol) in anhydrous dichloromethane (100 mL). After stirring at room temperature for 3 h, the reaction mixture was washed with water (75 mL), brine (50 mL), and concentrated under reduced pressure. The residue was purified by SiO2 column chromatography using 3% EtOAc/hexanes as eluent to give 12-(tert-butyldiphenylsilyloxy)dodec-1-yne (9.75 g, 88%) as a colorless oil. TLC: 6% EtOAc/hexanes, Rf≈0.7; 1H NMR (CDCl3, 300 MHz) δ 7.65-7.68 (m, 4H), 7.34-7.42 (m, 6H), 3.65 (t, J=7.3 Hz, 2H), 2.18 (dt, J=7.0, 2.4 Hz, 2H), 1.94 (t, J=1.9 Hz, 1H), 1.20-1.60 (m, 16H), 1.04 (s, 9H). the reaction mixture was washed with water (75 mL), brine (50 mL) concentrated under reduced pressure The residue was purified by SiO2 column chromatography

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

Procedure: Iodine (43.16 g, 170 mmol, 2.0 eq) was added to a suspension of distilled alcohol 61 (15.50 g, 85 mmol), imidazole (17.36 g, 255 mmol, 3.0 eq), and triphenylphosphine (66.90 g, 255 mmol, 3.0 eq) in dry toluene (425 mL, stored over molecular sieves). The reaction mixture was heated at reflux with vigorous stirring for 25 min, generating a yellow solution with a oily black precipitate. After cooling to 25°, saturated aqueous sodium bicarbonate (200 mL) and iodine (23.73 g, 93.5 mmol, 1.1 eq) were added and the reaction was stirred vigorously for 1 h. Saturated aqueous sodium sulfite (40 mL) was added, quenching the purple color. The reaction mixture was allowed to separate into two layers and the organic layer was washed with brine. The organic layer was dried over magnesium sulfate and concentrated. The residue was dissolved in dichloromethane (50 mL) and ether (200 mL) was added. After standing for 30 min, the resulting precipitate (triphenylphosphine oxide) was removed by filtration and washed with ether (100 mL). On further standing, the combined mother liquor and ether wash deposited a second crop of crystals which were removed as before. The combined mother liquors and ether washes were concentrated and dissolved in warm toluene (200 mL). This solution was placed on a silica gel column (500 g) and eluted with toluene (3 L) to afford 13.55 g, (55%) of iodide 62 as a pale yellow mobile liquid. This material was 96% one peak by GC. The reaction mixture was heated at reflux After cooling to 25° the reaction was stirred vigorously for 1 h quenching the purple color to separate into two layers the organic layer was washed with brine The organic layer was dried over magnesium sulfate concentrated The residue was dissolved in dichloromethane (50 mL) ether (200 mL) was added After standing for 30 min the resulting precipitate (triphenylphosphine oxide) was removed by filtration washed with ether (100 mL) On further standing, the combined mother liquor and ether wash were removed as before The combined mother liquors and ether washes were concentrated dissolved in warm toluene (200 mL) eluted with toluene (3 L)

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

Procedure: Iodine (43.16 g, 170 mmol, 2.0 eq) was added to a suspension of distilled alcohol 61 (15.50 g, 85 mmol), imidazole (17.36 g, 255 mmol, 3.0 eq), and triphenylphosphine (66.90 g, 255 mmol, 3.0 eq) in dry toluene (425 mL, stored over molecular sieves). The reaction mixture was heated at reflux with vigorous stirring for 25 min, generating a yellow solution with a oily black precipitate. After cooling to 25°, saturated aqueous sodium bicarbonate (200 mL) and iodine (23.73 g, 93.5 mmol, 1.1 eq) were added and the reaction was stirred vigorously for 1 h. Saturated aqueous sodium sulfite (40 mL) was added, quenching the purple color. The reaction mixture was allowed to separate into two layers and the organic layer was washed with brine. The organic layer was dried over magnesium sulfate and concentrated. The residue was dissolved in dichloromethane (50 mL) and ether (200 mL) was added. After standing for 30 min, the resulting precipitate (triphenylphosphine oxide) was removed by filtration and washed with ether (100 mL). On further standing, the combined mother liquor and ether wash deposited a second crop of crystals which were removed as before. The combined mother liquors and ether washes were concentrated and dissolved in warm toluene (200 mL). This solution was placed on a silica gel column (500 g) and eluted with toluene (3 L) to afford 13.55 g, (55%) of iodide 62 as a pale yellow mobile liquid. This material was 96% one peak by GC. The reaction mixture was heated at reflux After cooling to 25° the reaction was stirred vigorously for 1 h quenching the purple color to separate into two layers the organic layer was washed with brine The organic layer was dried over magnesium sulfate concentrated The residue was dissolved in dichloromethane (50 mL) ether (200 mL) was added After standing for 30 min the resulting precipitate (triphenylphosphine oxide) was removed by filtration washed with ether (100 mL) On further standing, the combined mother liquor and ether wash were removed as before The combined mother liquors and ether washes were concentrated dissolved in warm toluene (200 mL) eluted with toluene (3 L)

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

Procedure: The same procedure for 8-nonyn-1-ol was followed with 9-dodecyn-1-ol (4.68 g, 25.7 mmol), KH(3.09 g, 77.0 mmol), and 1,3-diaminopropane (70 mL). This produced 4.33 g of yellow oil (93%): IR (neat) ν 3317,2930, 2121 cm−1; 1H—NMR δ 3.62 (t, 2H, J=6.6 Hz), 2.17 (td, 2H, J=2.6 Hz, 7.1 Hz), 1.93 (t, 1H, J=2.6 Hz), 1.76 (bs, 1H), 1.55 (m, 4H), 1.28 bm, 12H); 13C—NMR δ 84.8, 68.0, 63.0, 32.7, 29.5, 29.4 (2C), 29.0, 28.7, 28.4, 25.7, 18.4; MS m/z 189.18 (M++Li).

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

Procedure: The same procedure for 8-nonyn-1-ol was followed with 9-dodecyn-1-ol (4.68 g, 25.7 mmol), KH(3.09 g, 77.0 mmol), and 1,3-diaminopropane (70 mL). This produced 4.33 g of yellow oil (93%): IR (neat) ν 3317,2930, 2121 cm−1; 1H—NMR δ 3.62 (t, 2H, J=6.6 Hz), 2.17 (td, 2H, J=2.6 Hz, 7.1 Hz), 1.93 (t, 1H, J=2.6 Hz), 1.76 (bs, 1H), 1.55 (m, 4H), 1.28 bm, 12H); 13C—NMR δ 84.8, 68.0, 63.0, 32.7, 29.5, 29.4 (2C), 29.0, 28.7, 28.4, 25.7, 18.4; MS m/z 189.18 (M++Li).

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

Procedure: Iodine (43.16 g, 170 mmol, 2.0 eq) was added to a suspension of distilled alcohol 61 (15.50 g, 85 mmol), imidazole (17.36 g, 255 mmol, 3.0 eq), and triphenylphosphine (66.90 g, 255 mmol, 3.0 eq) in dry toluene (425 mL, stored over molecular sieves). The reaction mixture was heated at reflux with vigorous stirring for 25 min, generating a yellow solution with a oily black precipitate. After colling to 25°, saturated aqueous sodium bicarbonate (200 mL) and iodine (23.73 g, 93.5 mmol, 1.1 eq) were added and the reaction was stirred vigorously for 1 h. Saturated aqueous Sodium sulfite (40 mL) was added, quenching the purple color. The reaction mixture was allowed to separate into two layers and the organic layer was washed with brine. The organic layer was dried over magnesium sulfate and concentrated. The residue was dissolved in dichloromethane (50 mL) and ether (200 mL) was added. After standing for 30 min, the resulting precipitate (triphenylphosphine oxide) was removed by filtration and washed with ether (100 mL). On further standing, the combined mother liquor and ether wash deposited a second crop of crystals which were removed as before. The combined mother liquors and ether washes were concentrated and dissolved in warm toluene (200 mL). This solution was placed on a silica gel column (500 g) and eluted with toluene (3 L) to afford 13.55 g (55%) of iodide 62 as a pale Yellow mobile liquid. This material was 96% one peak by GC. The reaction mixture was heated at reflux After colling to 25° the reaction was stirred vigorously for 1 h quenching the purple color to separate into two layers the organic layer was washed with brine The organic layer was dried over magnesium sulfate concentrated The residue was dissolved in dichloromethane (50 mL) ether (200 mL) was added After standing for 30 min the resulting precipitate (triphenylphosphine oxide) was removed by filtration washed with ether (100 mL) On further standing, the combined mother liquor and ether wash were removed as before The combined mother liquors and ether washes were concentrated dissolved in warm toluene (200 mL) eluted with toluene (3 L)

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

Procedure: tert-Butyldiphenylsilyl chloride (TBDPSCl, 8.70 g, 31.65 mmol) was slowly added to a 0° C. solution of dodec-11-yn-1-ol (4.80 g, 26.37 mmol) and imidazole (3.23 g, 47.47 mmol) in anhydrous dichloromethane (100 mL). After stirring at room temperature for 3 h, the reaction mixture was washed with water (75 mL), brine (50 mL), and concentrated under reduced pressure. The residue was purified by SiO2 column chromatography using 3% EtOAc/hexanes as eluent to give 12-(tert-butyldiphenylsilyloxy)dodec-1-yne (9.75 g, 88%) as a colorless oil. TLC: 6% EtOAc/hexanes, Rf≈0.7; 1H NMR (CDCl3, 300 MHz) δ 7.65-7.68 (m, 4H), 7.34-7.42 (m, 6H), 3.65 (t, J=7.3 Hz, 2H), 2.18 (dt, J=7.0, 2.4 Hz, 2H), 1.94 (t, J=1.9 Hz, 1H), 1.20-1.60 (m, 16H), 1.04 (s, 9H). the reaction mixture was washed with water (75 mL), brine (50 mL) concentrated under reduced pressure The residue was purified by SiO2 column chromatography

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

Procedure: Iodine (43.16 g, 170 mmol, 2.0 eq) was added to a suspension of distilled alcohol 61 (15.50 g, 85 mmol), imidazole (17.36 g, 255 mmol, 3.0 eq), and triphenylphosphine (66.90 g, 255 mmol, 3.0 eq) in dry toluene (425 mL, stored over molecular sieves). The reaction mixture was heated at reflux with vigorous stirring for 25 min, generating a yellow solution with a oily black precipitate. After cooling to 25°, saturated aqueous sodium bicarbonate (200 mL) and iodine (23.73 g, 93.5 mmol, 1.1 eq) were added and the reaction was stirred vigorously for 1 h. Saturated aqueous sodium sulfite (40 mL) was added, quenching the purple color. The reaction mixture was allowed to separate into two layers and the organic layer was washed with brine. The organic layer was dried over magnesium sulfate and concentrated. The residue was dissolved in dichloromethane (50 mL) and ether (200 mL) was added. After standing for 30 min, the resulting precipitate (triphenylphosphine oxide) was removed by filtration and washed with ether (100 mL). On further standing, the combined mother liquor and ether wash deposited a second crop of crystals which were removed as before. The combined mother liquors and ether washes were concentrated and dissolved in warm toluene (200 mL). This solution was placed on a silica gel column (500 g) and eluted with toluene (3 L) to afford 13.55 g, (55%) of iodide 62 as a pale yellow mobile liquid. This material was 96% one peak by GC. The reaction mixture was heated at reflux After cooling to 25° the reaction was stirred vigorously for 1 h quenching the purple color to separate into two layers the organic layer was washed with brine The organic layer was dried over magnesium sulfate concentrated The residue was dissolved in dichloromethane (50 mL) ether (200 mL) was added After standing for 30 min the resulting precipitate (triphenylphosphine oxide) was removed by filtration washed with ether (100 mL) On further standing, the combined mother liquor and ether wash were removed as before The combined mother liquors and ether washes were concentrated dissolved in warm toluene (200 mL) eluted with toluene (3 L)

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

Procedure: The same procedure for 8-nonyn-1-ol was followed with 9-dodecyn-1-ol (4.68 g, 25.7 mmol), KH(3.09 g, 77.0 mmol), and 1,3-diaminopropane (70 mL). This produced 4.33 g of yellow oil (93%): IR (neat) ν 3317,2930, 2121 cm−1; 1H—NMR δ 3.62 (t, 2H, J=6.6 Hz), 2.17 (td, 2H, J=2.6 Hz, 7.1 Hz), 1.93 (t, 1H, J=2.6 Hz), 1.76 (bs, 1H), 1.55 (m, 4H), 1.28 bm, 12H); 13C—NMR δ 84.8, 68.0, 63.0, 32.7, 29.5, 29.4 (2C), 29.0, 28.7, 28.4, 25.7, 18.4; MS m/z 189.18 (M++Li).