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Experimental Procedure
for the Synthesis of 19 and 20: To a degassed solution of 10 (300 mg, 0.64 mmol) and n-Bu4NOAc (484 mg, 1.60 mmol)
in DMF/CH3CN/H2O (5:5:1)
(10 mL) was added under a nitrogen atmosphere trans-di(µ-acetato)-bis[o-(di-o-tolylphosphino)-benzyl]dipalladium(II)
(12 mg, 2 mol%) and the mixture was stirred at 120 °C
under reflux for 4 h. After cooling, H2O (40 mL) was
added; the resulting mixture was extracted with Et2O
(3 × 25 mL), washed with brine, dried over MgSO4 and concentrated
in vacuo. Purification by column chromatography (silica gel, CH2Cl2/petrol
ether = 6/4) and repeated chromatography
using AgNO3-coated silica gel (CH2Cl2)
afforded 149 mg (60%) of 19 as
a colorless oil and 35 mg (14%) of 20 as
white crystals.
Selected data for 19: [α]D
20 +22.7
(c 1.0, CHCl3). 1H
NMR (500 MHz, CDCl3, TMS): δ = 1.23
(s, 3 H, 18-H), 1.10-2.40 (m, 10 H), 2.76 (d, 1 H), 2.80
(m, 2 H, 6-H), 3.58 (d, 1 H, J = 15.2
Hz, 17b-H), 3.76 (s, 3 H, 3-OMe), 4.57 (d, 1 H, J = 15.2
Hz, 17b-H), 4.92 (s, 1 H, 16a-H), 5.28 (s, 1 H, 16a-H), 6.62 (d,
1 H, J = 2.6
Hz, 4-H), 6.73 (dd, 1 H, J = 8.6
Hz, 2.6 Hz, 2-H), 7.02-7.24 (m, 5 H, 1-H, 3′-H,
4′-H, 5′-H and 6′-H). 13C
NMR (125 MHz, CDCl3, TMS): δ = 14.2
(C-18), 26.2 and 26.4 (2 C, C-11 and C-12), 29.9 (C-6), 37.3, 40.3, 41.2,
41.9, 42.9, 44.1 (C-17b), 53.0 (C-13), 55.2 (3-OCH3), 111.7
(C-2), 113.4 (C-4), 120.7 (C-16a), 126.2, 126.5, 127.1, 129.0, 130.2,
132.0 (C-10), 134.0, 137.7 (C-5), 141.1, 147.4 (C-16), 157.7 (C-3),
215.3 (C-17c).
19 Crystallographic data for 4 and 20 can be
obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html
or from the Cambridge Crystallographic Data Centre CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK. Deposition numbers: CCDC 168413 for 4 and CCDC 168412 for 20.
20 Selected data for 12: [α]D
20 -28
(c 1.0, CHCl3). Mp 173-175 °C. 1H
NMR (500 MHz, CDCl3, TMS): δ = 1.01
(s, 3 H, 18-H), 1.10-2.50 (m, 13 H), 2.88 (m, 2 H, 6-H),
3.12 (d, 1 H, J = 11.9
Hz, 17c-H), 3.79 (s, 3 H, CH3O), 4.00 (d, 1 H, J = 10.0 Hz,
17d-H), 5.99 (dt, 1 H, J = 15.5, J = 6.2 Hz,
16-H), 6.62 (d, 1 H, J = 15.5
Hz, 17-H), 6.65 (d, 1 H, J = 2.7
Hz, 4-H), 6.74 (dd, 1 H, J = 8.6
Hz, 2.7 Hz, 2-H), 7.08-7.37 (m, 5 H, 1-H, 3′-H,
4′-H, 5′-H, 6′-H). 13C
NMR (125 MHz, CDCl3): δ = 17.8 (C-18),
25.7 (C-11), 28.1 (C-7), 30.4, 30.5, 32.4, 35.8, 41.1, 42.2 (C-8),
43.1 (C-9), 44.8 (C-14), 55.2 (CH3O), 73.6 (C-17d), 111.6
(C-2), 113.5 (C-4), 126.3, 126.6, 126.9 (2C), 127.1, 131.4, 133.0
(C-10), 135.7, 136.2, 137.3, 138.1 (C-5), 157.5 (C-3).