3. 2s, Chloromethyl)diisopropylsilyl)oxy)-3-(2-methylallyl)-2-((R)-1-(2,4,6-triisopropyl phenyl)ethoxy)hexahydroindolizin-5(1H)-one (135)

, 1 equiv) and DMAP (45 mg, 0.37 mmol, 0.18 equiv) were added and the solution was stirred

, IR (film): ?3582, pp.1070-1071, 1458.

H. Nmr,

C. Nmr, CDCl 3 , 125 MHz): ? 168.1 (C), 148.3 (C), 147.3 (C), 144.6 (C), 143.8 (C), 134.0 (C), 123.1 (CH), 120.3 (CH), vol.111

, MS (ESI): m/z 640.42 (MNa + , 100%), 618.42 (MH + )

, HRMS calcd for C 36 H 61 NO 3 SiCl: 618.4109. Found: 618.4123 (MH + )

, MS (ESI): m/z 582.45 (MH + , 100%), vol.604

, Hydroxydiisopropylsilyl)methyl)-7-methylene-1-((R)-1-(2,4,6-triisopropylphenyl)ethoxy)decahydro-1H-pyrrolo[2,1,5-de]quinolizin-3-ol (146), vol.136

, 10 equiv) in 200 µl hexane at 0°C. The mixture was stirred at RT for 7h, after which the reaction mixture was concentrated in vacuo. Formic acid (200 µl) was then added and stirred at RT. After 1 h, the mixture was diluted with Et 2 O and quenched with saturated K 2 CO 3 solution till reaching alkaline pH

, IR, vol.3389, pp.1119-1120, 1261.

H. Nmr, CDCl 3 , 400 MHz): ? 7.03 (s, 1H), vol.6

, Hz, 1H), 3.11?3.19 (m, 2H), 2.85 (sept, J= 6.9 Hz, 1H), vol.2

, ?1.20 (m, 1H), 1.65?1.79 (m, 4H), vol.1

C. Nmr,

, MS (ESI): m/z 566.6 (MH + , 100%)

, HRMS calcd for C 36 H 60 NO 2 Si: 566.4393. Found: 566.44 (MH + )

, 8R,8aR)-8-Hydroxy-6-((hydroxydiisopropylsilyl)methyl)-4-methyl-2-((R)-1-(2,4,6-triisopropylphenyl)ethoxy)decahydro-1H-pyrrolo

, J= 13.1, 13.1 Hz, 1H), 1.96 (br peak, 1H), 1.58?1.76 (m, 5H), vol.1

C. Nmr, 125 MHz): ? 160.3 (CH), 148.8 (C), 147.2 (C), 146.0 (C), 133.2 (C), 123.1 (CH), 120.2 (CH), 85.2 (C), vol.74

, CH), 28.0 (CH, vol.33

, MS (ESI): m/z 612.6 (MH + , 100%)

, ,4,6-triisopropylphenyl)ethoxy)decahydro-1H-pyrrolo[2,1,5-de]quinolizine-3,7-diol (143). K 2 CO 3 (280 mg, 2.03 mmol, 13.5 equiv) was added to a solution of formate 139 (94.0 mg, 0.15 mmol, 1.0 equiv) in 2.7 ml MeOH and stirred for 1h at RT. Then the reaction was diluted with DCM and quenched with brine, Hydroxydiisopropylsilyl)methyl)-7-methyl-1-((R)-1

, IR, vol.3408, pp.1082-1083, 1112.

H. Nmr, 500 MHz): ? 7.26 (d, J= 1.8 Hz, 1H), vol.7

, Hz, 1H), 2.95 (t, J= 7.9 Hz, 1H), 2.89(ddd, J= 3.9, 6.4, 12.2 Hz, 1H), 2.80 (sept, J= 6.9 Hz, 1H), vol.2

C. Nmr,

, MS (ESI): m/z 472.4 (MH + , 100%)

(. 2s, KOt-Bu (1.2 g, 10.7 mmol, ~12 equiv) and TBAF (1M in THF, 6.3 ml, 6.3 mmol, ~7 equiv) were added to a solution of 560

D. , The reaction mixture was stirred for 9h at 120°C. The mixture was then diluted with Et 2 O and quenched with water. The aqueous layer was extracted with Et 2 O 3 times. The combined organic layers were dried over MgSO 4, p.26

, sept, J= 6.9 Hz, 1H), 2.73 (app dd, J= 2.9, 13.0 Hz, 1H), 2.13 (ddd, J= 8.5, 8.5, 12.7 Hz, 1H), 1.97 (br s, 1H), 1.83 (dd, J= 13.0, 13.0 Hz, 1H), 1.78?1.84 (m, 1H), vol.86

C. Nmr, CDCl 3 , 125 MHz): ? 148.8 (C), 147.2 (C), 145.9 (C), 133.2 (C), 123.1 (CH), vol.120, pp.70-77

, 2 (CH), 28.0 (CH), vol.33

, MS (ESI): m/z 558.51 (MH + , 100%)

, HRMS calcd for C 33 H 56 NO 4 Si: 558.3979. Found: 558.3987 (MH + )

, To a solution of alcohol 75

H. Nmr, , vol.1

, ?1.90 (m, 1H), 1.55?1.75 (m, 3H), vol.1

, HRMS calcd for C 31 H, vol.52

, To a stirred solution of 75 (5.5 mg, 0.012 mmol, 1 equiv) in 180 µl DCM were added Et 3 N (30 µl, 0.21 mmol, 17.5 equiv) and MsCl (10 µl, 0.14 mmol, 11.7 equiv) at ambient temperature. The mixture was stirred for 4h at room temperature and followed by TLC till the consumption of all the starting materials, vol.4

, IR (film): ? 2957, pp.1112-1113, 1176.

H. Nmr, CDCl 3 , 500 MHz): ? 7.03 (d, J= 1.6 Hz, 1H), 6.95 (d, J= 1.6 Hz, 1H), 5.06 (q, J= 6.7 Hz

C. Nmr,

, MS (ESI): m/z 610.37 (MH + , 100%)

, HRMS calcd for C 32 H 52 NO 6 S 2 : 610.32306. Found: 610.32244 (MH + )

, Butyldimethylsilyl)oxy)-4,6-dimethyl-2-((R)-1-(2,4,6-triisopropyl phenyl)ethoxy)decahydro-1H-pyrrolo

, equiv) in dry DCM (300 µl) were added Et 3 N (30 µl, 0.215 mmol, 12.6 equiv) and DMAP (4 mg, 0.032 mmol, 1.8 equiv) at room temperature. Tertbutyldimethylsilyl chloride (40 mg, 0.266 mmol, 15.6 equiv) was also added in 2 portions with 3h30min interval. The reaction mixture was stirred for 7h at 60°C, quenched with water and diluted with pentane

H. Nmr, CDCl 3 , 400 MHz): ? 7.02 (d, J= 2.0 Hz, 1H), 6.91 (d, J= 2.0 Hz, 1H), 5.08 (q, J= 6.9 Hz

, To a THF solution (500 µl) of the silylated alcohol 172 (5.8 mg, 9.2*10 -3 mmol, 1.0 equiv) was added 40 mg of TBAF.H 2 O (0.14 mmol, 15 equiv) at RT. The reaction mixture was stirred for 24h before diluting with Et 2 O and quenching with water

H. Nmr, CDCl 3 , 400 MHz): ? 7.03 (d, J= 1.9 Hz, 1H), 6.93 (d, J= 1.9 Hz, 1H), 5.00 (q, J= 6.8 Hz, 1H), 3.94(ddd

, MS (ESI): m/z 514.38 (MH + , 100%)

, HRMS calcd for C 32 H, vol.52

, A solution of oxalyl chloride (5 µl, 0.06 mmol, equiv) was injected slowly and the reaction was allowed to warm slowly to ?20°C over 1h. Meanwhile, a mixture of 170 mg of TBTSO 2 CH 3 S8 (0.83 mmol) and 830 µl of freshly prepared LiHMDS solution (0.95 M in THF, 0.79 mmol) in 450 µl THF was stirred for 30 min at ?80°C<T<?60°C. The reaction bath was cooled back to ?80°C and the reaction was treated with a freshly prepared solution of TBTSO 2 CH 2 Li

, IR, vol.3399, pp.1120-1121, 1155.

H. Nmr, CDCl 3 , 500 MHz): ? 7.03 (d, J= 1.7 Hz, 1H), 6.90 (d, J= 1.8 Hz 1H), 5.23 (ddd, J= 2.5, 2.5, 5.0 Hz, 1H), 5.00 (q, J= 6.8 Hz, 1H)

C. Nmr,

, MS (ESI): m/z 596.29 (MH + , 100%)

, HRMS calcd for C 35 H 58 N 5 O 3 : 596.4534. Found: 596.4526 (MH + )

, A solution of n-BuLi in hexane (2.5 M, 75 µl, 0.1875 mmol, 8.8 equiv) was added to a solution of methyltriphenylphosphonium bromide (77 mg, 0.215 mmol, 10.1 equiv) in 0.3 ml THF at 0°C. The resulting yellow suspension was stirred for 30 min

H. Nmr, CDCl 3 , 400 MHz): ? 7.00 (s, 1H), 6.91 (s, 1H), 5.04 (q, J= 6.8 Hz, 1H), vol.3, p.99

. Hz,

, 250 µl i-PrOH were added phenyl silane (60 µl, 0.486 mmol, 48.0 equiv), pp.tert-butyl

, Mn(dpm) 3 (2 mg, 3.3*10 ?3 mmol, 33% by mole) at RT. The reaction mixture was stirred for 4h then the solvent was evaporated. The crude mixture was directly loaded on silica gel eluted with 1%

H. Nmr, CDCl 3 , 500 MHz): ? 7.00 (d, J= 1.9 Hz, 1H), 6.90 (d, J= 1.9 Hz, 1H), 5.00 (q, J= 6.8 Hz, 1H), vol.3

1. Hz, , vol.1

, MS (ESI): m/z 470.39 (MH + , 100%)

, HRMS calcd for C 31 H, vol.52

H. Nmr,

. Hz,

. O-, 1S,2aR,3S,5S,5aR,7R,8aS)-7-Hydroxy-3,5,7-trimethyldecahydro-1H-pyrrolo

O. Carbonothioate, To a solution of the diol 150 (5.0 mg, 0.021 mmol, 1.0 equiv) in 250 µl DCM were added DMAP (10.0 mg, 0.082 mmol, 3.9 equiv) and O-phenyl chlorothionoformate (7.0 µl, 0.051 mmol, 2.4 equiv). The reaction mixture was stirred for 5h at RT and then quenched with 10% NaOH and diluted with DCM

H. Nmr, CDCl 3 , 500 MHz): ? 7.39?7.45 (m, 2H), 7.27?7.31 (m, 1H), 7.07?7.12 (m, 2H)

. Hz,

, To a