Métodos de medición de las Variables Climáticas (IDEAM, 2005)

(Z)-5-(tert-butyldiphenylsilyloxy)-2-cyclohexyl-1- p-tolylpent-2-en-1-ol (1-56). A dry 10 mL Schlenk flask, which was evacuated under vacuum and backfilled with N2 (g) three times, was charged with dicyclohexylborane (1 mmol) and

toluene (1 mL) under a nitrogen atmosphere. The solution was cooled to 0 ºC followed by addition of (4-bromobut-3-ynyloxy)(tert-butyl)diphenylsilane (386.4 mg, 1 mmol). The reaction was stirred for 5 min, warmed to room temperature, and stirred for 15 min. The solution was cooled to –78 °C and diethylzinc (3 mL, 3 mmol, 1.0 M in toluene) was added. After stirring for 20 min, the reaction flask was warmed to 0 ºC. Under a steady flow of N2 (g), the rubber septum was replaced with a glass stopper coated with silicon

grease and high vacuum was gradually applied to remove the volatile contents. The resulting vinylzinc reagent was redissolved in toluene (1 mL) followed by addition of p- tolualdehyde (0.67 mmol). The reaction mixture was gradually warmed to ambient temperature and stirred until no aldehyde remained by TLC (usually 7-16 h). Quenching by saturated aq. NH4Cl (2 mL), followed by addition of 2 N HCl (1 mL) and 5 mL of

EtOAc. The organic layer was separated and the aqueous layer was extracted successively with EtOAc (2 × 10 mL). The combined organic layers were successively washed with saturated NaHCO3 and brine, dried over MgSO4, and filtered. The filtrate

was concentrated in vacuo and the residue was purified by column chromatography on silica gel to yield a mixture of 1-56 (173 mg, 50.7%) and (Z)-5-(tert- butyldiphenylsilyloxy)-2-ethyl-1-p-tolylpent-2-en-1-ol (1-53) (11.0 mg, 3.6%) in a 14:1 ratio, respectively. When diethylzinc was added to the reaction solution at 0 °C, the ratio changed to 4:1. 1 H NMR (CDCl3, 500 MHz): δ 7.72 (m, 4H), 7.44 (m, 6H), 7.31 (d, J = 7.9 Hz, 2H), 7.14 (d, J = 7.9 Hz, 2H), 5.54 (d, 4.0 Hz, 1H), 5.48 (t, J = 7.8 Hz, 1H), 3.69 (m, 2H), 2.61 (m, 1H), 2.37 (s, 3H), 1.96 (m, 1H), 1.79 (m, 2H), 1.68 (m, 2H), 1.51 (d, J = 9.4 Hz, 1H), 1.28 (m, 2H), 1.11 (s, 9H) ppm; 13 C{1 H} NMR (CDCl3, 125 MHz): δ 149.9, 140.5, 136.4, 135.9, 133.7, 129.9, 128.9, 127.9, 126.1, 123.2, 72.6, 63.9, 41.6, 34.6, 34.3, 31.4, 27.2, 26.5, 21.3, 19.4 ppm; HRMS-CI calcd for C34H44O2SiCl (M+Cl)

-

: 547.2797, found 547.2799.

(Z)-5-(tert-butyldiphenylsilyloxy)-2-ethyl-1-p- tolylpent-2-en-1-ol (1-53). A dry 10 mL Schlenk flask, which was evacuated under vacuum and backfilled with N2 (g) three times, was

charged with (4-bromobut-3-ynyloxy)(tert-butyl)diphenylsilane (128.13 mg, 0.33 mmol) and toluene (1 mL) under a nitrogen atmosphere. The solution was cooled to 0 ºC followed by slow addition of diethylborane (0.33 mL, 1.0 M in toluene, 0.33 mmol). The reaction was stirred for 5 min, warmed to room temperature, and stirred for 15 min. The

solution was cooled to –78 °C and diisopropylzinc (1 mL, 1.0 M in toluene 1 mmol) was added. After stirring for 20 min, the reaction flask was warmed to 0 ºC. Under a steady flow of N2 (g), the rubber septum was replaced with a glass stopper coated with silicon

grease and high vacuum was gradually applied to remove the volatile contents. The resulting vinylzinc reagent was redissolved in toluene (1 mL) followed by addition of p- tolualdehyde (0.22 mmol). The reaction mixture was gradually warmed to ambient temperature and stirred until no aldehyde remained by TLC (usually 7-16 hrs). It was quenched with saturated aq. NH4Cl (2 ml), followed by the addition of 2 N HCl (1 mL)

and 5 mL of EtOAc. The organic layer was separated and the aqueous layer was extracted successively with EtOAc (2 × 10 mL). The combined organic layers were successively washed with saturated NaHCO3 and brine, dried over MgSO4, and filtered.

The filtrate was concentrated in vacuo and the residue was purified by column chromatography on silica gel to yield a mixture of 1-53 (48 mg, 47.5%) and (Z)-5-(tert- butyldiphenylsilyloxy)-2-isopropyl-1-p-tolylpent-2-en-1-ol (1-54) (10.0 mg, 9.6%) in a 5:1 ratio, respectively. 1 H NMR (CDCl3, 500 MHz): δ 7.72 (d, J = 7.8 Hz, 4H), 7.44 (m, 6H), 7.26 (d, J = 7.9 Hz, 2H), 7.14 (d, J = 7.9 Hz, 2H), 5.63 (d, J = 3.0 Hz, 1H), 5.42 (t, J =7. 6 Hz, 1H), 3.74 (t, J = 6.4 Hz, 2H), 2.6 (m, 1H), 2.51 (m, 1H), 2.37 (s, 3H), 2.30 (d, J = 3.5 Hz, 1H), 2.10 (m, 1H), 1.87 (m, 1H), 1.10 (s, 9H), 0.99 (t, J = 7.4 Hz, 3H) ppm; 13 C{1 H} NMR (CDCl3, 125 MHz): δ 144.9, 140.0, 136.6, 133.8, 129.9, 129.0, 127.9, 126.7, 126.0, 122.8, 72.1, 64.0, 31.2, 27.1, 24.6, 21.3, 19.4, 13.0 ppm.

(Z)-2-(3-(tert-butyldiphenylsilyloxy)propylidene)- 1-p-tolylhexan-1-ol (1-55). A dry 10 mL Schlenk flask, which was evacuated under vacuum and backfilled with N2 (g) three times, was charged with (4-bromobut-3-ynyloxy)(tert-

butyl)diphenylsilane (386.4 mg, 1 mmol) and toluene (1 mL) under a nitrogen atmosphere. The solution was cooled to 0 ºC followed by slow addition of diethylborane (1 mL, 1.0 M in toluene, 1 mmol). The reaction was stirred for 5 min, warmed to room temperature, and stirred for 15 min. The solution was cooled to –78 °C and dibutylzinc (3 mL, 1.0 M in heptane, 3 mmol) was added. After stirring for 20 min, the reaction flask was warmed to 0 ºC. Under a steady flow of N2 (g), the rubber septum was replaced with

a glass stopper coated with silicon grease and high vacuum was gradually applied to remove the volatile contents. The resulting vinylzinc reagent was redissolved in toluene (1 mL) followed by addition of p-tolualdehyde (0.67 mmol). The reaction mixture was gradually warmed to ambient temperature and stirred until no aldehyde remained by TLC (usually 7-16 hrs). It was quenched with saturated aq. NH4Cl (2 ml), followed by the

addition of 2 N HCl (1 mL) and 5 mL of EtOAc. The organic layer was separated and the aqueous layer was extracted successively with EtOAc (2 × 10 mL). The combined organic layers were successively washed with saturated NaHCO3 and brine, dried over

MgSO4, and filtered. The filtrate was concentrated in vacuo and the residue was purified

by column chromatography on silica gel to yield a mixture of 1-55 (55 mg, 15.7%) and 1- 53 (205 mg, 62%) in a 1:4 ratio, respectively. 1

H NMR (CDCl3, 500 MHz): δ 7.71 (d, J

= 2.7 Hz, 1H), 5.42 (t, J = 7.4 Hz, 1H), 3.73 (t, J = 6.2 Hz, 2H), 2.59 (m, 1H), 2.49 (m, 1H), 2.36 (s, 3H), 2.29 (d, 3.5 Hz, 1H), 2.03 (m, 1H), 1.88 (m, 1H), 1.29 (m, 4H), 1.09 (s, 9H), 0.86 (t, J = 7.1 Hz, 3H); 13 C{1 H} NMR (CDCl3, 125 MHz): δ 143.6, 140.0, 136.6, 135.9, 133.8, 129.9, 129.0, 127.9, 126.0, 123.9, 72.2, 64.0, 31.9, 31.3, 31.2, 27.1, 22.9, 21.3, 19.4, 14.2. (Z)-5-(tert-butyldiphenylsilyloxy)-2-methyl-1-p- tolylpent-2-en-1-ol (1-52). A dry 10 mL Schlenk flask, which was evacuated under vacuum and backfilled with N2 (g) three times, was

charged with (4-bromobut-3-ynyloxy)(tert-butyl)diphenylsilane (386.4 mg, 1 mmol) and toluene (1 mL) under a nitrogen atmosphere. The solution was cooled to 0 ºC followed by slow addition of diethylborane (1 mL, 1.0 M in toluene, 1 mmol). The reaction was stirred for 5 min, warmed to room temperature, and stirred for 15 min. The solution was cooled to –78 °C and dimethylzinc (3 mL, 1.0 M, in toluene, 3 mmol) was added. After stirring for 20 min, the reaction flask was warmed to 0 ºC. Under a steady flow of N2 (g),

the rubber septum was replaced with a glass stopper coated with silicon grease and high vacuum was gradually applied to remove the volatile contents. The resulting vinylzinc reagent was redissolved in toluene (1 mL) followed by addition of p-tolualdehyde (0.67 mmol). The reaction mixture was gradually warmed to ambient temperature and stirred until no aldehyde remained by TLC (usually 7-16 hrs). It was quenched by saturated aq. NH4Cl (2 mL), followed by the addition of 2 N HCl (1 mL) and 5 mL of EtOAc. The

EtOAc (2 × 10 mL). The combined organic layers were successively washed with saturated NaHCO3 and brine, dried over MgSO4, and filtered. The filtrate was

concentrated in vacuo and the residue was purified by column chromatography on silica gel to yield a mixture of 1-52 (67.6 mg, 23%) and 1-53 (172.2 mg, 56.7%) in a 1:2.5 ratio, respectively. 1 H NMR (CDCl3, 500 MHz): δ 7.75 (d, J = 7.1 Hz, 4H), 7.45 (m, 6H), 7.25 (d, J = 7.9 Hz, 2H), 7.15 (d, J = 7.8 Hz, 2H), 5.62 (s, 1H), 5.40 (t, J = 7.4 Hz, 1H), 3.76 (m, 2H), 2.55 (dt, J = 6.7 Hz, 6.4 Hz, 2H), 2.37 (s, 3H), 2.08 (d, J = 3.1 Hz, 1H), 1.62 (s, 3 H), 1.12 (s, 9H) ppm; 13 C{1 H} NMR (CDCl3, 125 MHz): δ 139.6, 139.1, 136.6, 135.8, 133.9, 129.9, 129.1, 127.9, 125.9, 124.7, 71.5, 64.0, 31.3, 27.1, 21.3, 19.4, 18.5 ppm; HRMS-CI calcd for C29H36O2SiCl (M+Cl

+

): 479.2195, found 479.2189.

1.6.7.2. Protonolysis of Intermediates in the Generation of Trisubstituted