R
SYNTHETIC COMMUNICATIONSV
5
chromatography (ethyl acetate/hexane 1:9) to furnish product 12 (203 mg, 0.70 mmol,
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93%) as a colorless liquid; [a]D ꢀ13.44 (c 1.0, CHCl3); IR (CH2Cl2) ꢀ: 2921, 2850,
1
1605, 1465, 1053 cmꢀ1; H NMR (400 MHz, CDCl3) d: 7.38–7.28 (m, 5H), 4.84 (d,
J ¼ 11.88 Hz, 1H), 4.58 (d, J ¼ 11.88 Hz, 1H), 3.03–3.02 (m, 2H), 2.79 (t, J ¼ 4.12 Hz,
1H), 2.49 (dd, J ¼ 5.04, 2.28 Hz, 1H), 1.71–1.62 (m, 1H), 1.57–1.42 (m, 1H), 1.25 (br s,
14H), 0.88 (t, J ¼ 6.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) d: 138.6, 128.3, 127.8, 127.5,
80.5, 71.7, 55.1, 43.2, 32.3, 31.9, 29.6, 29.5, 29.4, 29.3, 25.5, 22.7, 14.1; HRMS (ESI),
calcd for C19H30O2Na [M þ Na]þ 313.2143; found 313.2140.
(2S,3S)-3-(benzyloxy)dodecan-2-ol, 13
To a solution of epoxide 12 (150 mg, 0.52 mmol) in dry THF (5 mL) under nitrogen
atmosphere at 0 ꢁC was added LiAlH4 (59 mg, 1.55 mmol) portion wise. The resulting
suspension was continued to stir at room temperature for 3 h. Then reaction mixture
was quenched with 10% aqueous NaOH and diluted with EtOAc. The organic layer was
separated and aq. layer was extracted with EtOAc (3 ꢂ 15 mL). The collective organic
layer was dried over anhydrous Na2SO4 and concentrated in vacuo to afford crude com-
pound. The crude compound was purified using silica gel chromatography (Rf ¼ 0.4,
EtOAc/hexane 1:9 v/v) to afford alcohol 13 (128 mg, 0.44 mmol, 85%) as a colorless
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liquid; [a]D ꢀ8.33 (c 1.0, CHCl3); IR (CH2Cl2) ꢀ: 3465, 2931, 2859, 1609, 1095, 1045,
975, 914, 837 cmꢀ1 1H NMR (400 MHz, CDCl3) d: 7.38–7.28 (m, 5H), 4.67 (d,
;
J ¼ 11.4 Hz, 1H), 4.59 (d, J ¼ 11.4 Hz, 1H), 3.78–3.70 (m, 1H), 3.22 (q, J ¼ 11.44,
5.48 Hz, 1H), 2.47 (d, J ¼ 4.12 Hz, 1H), 1.64–1.46 (m, 2H), 1.28 (br s 13 H), 1.18 (d,
J ¼ 6.4 Hz, 3H), 0.88 (t, J ¼ 6.88 Hz, 3H); 13C NMR (100 MHz, CDCl3) d: 138.3, 128.5,
127.8, 127.6, 84.1, 72.4, 68.9, 31.9, 30.1, 29.9, 29.5, 29.3, 24.8, 22.7, 18.9, 14.1; HRMS
(ESI), calcd for C19H32O2Na [M þ Na]þ 315.2300; found 315.2294.
((((2R,3S)-2-azidododecan-3-yl)oxy)methyl)benzene, 14
To a stirred solution of alcohol 13 (80 mg, 0.27 mmol) in dry DCM (5 mL) was added
Et3N (49 mL, 0.35 mmol) at 0 ꢁC under N2 atmosphere. After the mixture was stirred for
5 min, MsCl (25 mL, 0.32 mmol) was added and stirring was continued for 30 min at
room temperature. After completion of the reaction, reaction was diluted with H2O and
the aq. layer was extracted with CH2Cl2 (3 ꢂ 15 mL). The combined organic layers were
washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced
pressure. The crude compound was used as such for the next step without further
purification.
NaN3 (53 mg, 0.82 mmol) was added to a solution of above crude in dry DMF (5 mL)
under nitrogen atmosphere and stirred reaction mixture for 12 h at 70 ꢁC. The reaction
mixture was being cooled to room temperature, diluted with water and extracted with
Et2O (3 ꢂ 10 mL). The combined organic layer was washed with brine, dried over
anhydrous Na2SO4 and concentrated under reduced pressure. Purification using silica
gel chromatography (EtOAc/hexane 1:49) afforded azide 14 (77 mg, 0.24 mmol, 89%) as
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a colorless oil; [a]D ꢀ24.55 (c 1.0, CHCl3); IR (CH2Cl2) ꢀ: 2935, 2859, 2109, 1659,
975, 914, 837 cmꢀ1 1H NMR (400 MHz, CDCl3) d: 7.37–7.28 (m, 5H), 4.65 (d,
;