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°C and DIBAL-H (0.440 mL of a 1.0M solution in hexanes, 0.440 mmol), was added dropwise.
The reaction was allowed to warm up to rt over a period of 1 h, when it was quenched by
addition of MeOH (0.1 mL) and sat’d aq. NH4Cl (0.5 mL). Vigorous stirring for 10 min led to
formation of white solid that was filtered on a fritted funnel and washed with excess CH2Cl2. The
filtrate was concentrated under vacuum, and the crude residue was purified by flash
chromatography (hexanes-EtOAc, 4 : 1, v/v) to afford 183 (30 mg, 65%).
1 H NMR (300 MHz, CDCl3): δ 7.39-7.33 (m, 5H), 6.34 (dd, J = 17.2, 10.7 Hz, 1H), 5.69 (q, J =
7.0 Hz, 1H), 5.46-5.40 (m, 2H), 5.22-5.13 (m, 2H), 4.71 (d, J = 14.3 Hz, 1H), 3.97-3.90 (m, 1H),
3.78 (d, J = 14.3 Hz, 1H), 3.66 (d, J = 9.0 Hz, 1H), 1.76 (d, J = 7.0 Hz, 3H), 1.43 (s, 3H). 13 C
NMR (75 MHz, CDCl3): δ 155.8, 136.7, 136.4, 134.5, 130.2, 129.4, 128.5, 128.0, 127.7, 122.1,
116.8, 69.0, 67.3, 61.5, 41.3, 20.2, 13.4; IR (thin film): ν 3427, 2927, 1685, 1406 cm -1 ; MS m/z
(%) 313 (32), 282 (45), 238 (29), 192 (30), 91 (100); EI-HRMS calcd for C18H20NO2 m/z [M-
31] + 282.1494; found 282.1485.
Cbz
O
N
O
6-Acryloyloxymethyl-3-ethylidene-6-methyl-4-vinyl-3,6-dihydro-2H-pyridine-1-carboxylic
acid benzyl ester (184). To a solution of alcohol 183 (30 mg, 0.096 mmol), in CH2Cl2 (0.5 mL)
was added Et3N (0.016 mL, 0.11 mmol), followed by acryloyl chloride (0.010 mL, 0.11 mmol) at
rt. After 10 min at rt, the reaction was diluted with benzene (0.5 mL) and purified by flash
chromatography (hexanes-EtOAc, 9 : 1, v/v) to afford ester 184 (18 mg, 51%).
1 H NMR (300 MHz, CDCl3): δ 7.38-7.34 (m, 5H), 6.37-6.28 (m, 1H), 6.31 (dd, J = 17.3, 1.6 Hz,
1H), 6.04 (dd, J = 17.3, 10.4 Hz, 1H), 5.77 (dd, J = 10.4, 1.6 Hz, 1H), 5.66 (q, J = 7.1 Hz, 1H),
184
227