Triethylsilane → 2-oxo-2-((10S,13S,16R,17S)-10,13,16-trimethyl-3-oxo-2,3,6,7,8,10,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-17-yl)ethyl acetate

HRID 1496724

Reaction equation

HRID 1496724 reaction equation
[C:1]([O:4][CH2:5][C:6](=[O:28])[C@@H:7]1[C@:23]2([CH3:24])[CH:10]([CH:11]3[C:20](=[CH:21][CH2:22]2)[C@:19]2([CH3:25])[C:14](=[CH:15][C:16](=[O:26])[CH:17]=[CH:18]2)[CH2:13][CH2:12]3)[CH2:9][C@H:8]1[CH3:27])(=[O:3])[CH3:2].C([SiH](CC)CC)C>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Rh].C(Cl)Cl>[C:1]([O:4][CH2:5][C:6](=[O:28])[C@@H:7]1[C@:23]2([CH3:24])[CH:10]([CH:11]3[C:20](=[CH:21][CH2:22]2)[C@:19]2([CH3:25])[C:14](=[CH:15][C:16](=[O:26])[CH2:17][CH2:18]2)[CH2:13][CH2:12]3)[CH2:9][C@H:8]1[CH3:27])(=[O:3])[CH3:2]

Participants

5

Reactant 2

HCID 12052TriethylsilaneHCID 592717402-oxo-2-((10S,13S,16R,17S)-10,13,16-trimethyl-3-oxo-6,7,8,10,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-17-yl)ethyl acetate

Product 1

HCID 534920562-oxo-2-((10S,13S,16R,17S)-10,13,16-trimethyl-3-oxo-2,3,6,7,8,10,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-17-yl)ethyl acetateYield 30%

Reagents, catalysts & solvents 2

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)CatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

A mixture of 3.3 g (8.6 mM) of 2-oxo-2-((10S,13S,16R,17S)-10,13,16-trimethyl-3-oxo-6,7,8,10,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-17-yl)ethyl acetate, chlorotris(triphenylphosphine)rhodium(I) (Wilkinson's Catalyst, 480 mg, 0.52 mM), triethylsilane (1.4 mL, 1.0 g, 8.8 mM) and methylene chloride (15 mL) was warmed to 40° C. and stirred until most of the starting material was gone, as determined by thin layer chromatography. The reaction was evaporated in vacuo and chromatographed on fine silica gel (600 g) in 10-15% ethyl acetate in methylene chloride. One fraction of 700 mL was collected, followed by twelve 200 mL fractions. A 1.0 g quantity of desired product (30% yield) was obtained by evaporation of fractions 6-12. (Starting material was obtained from fraction 13, 0.7 g, 20% recovery). NMR (500 MHz, CDCl3, TMS): δ 0.68 (s, 3H), 0.98 (d, 3H, J=6.5 Hz), 1.12 (m, 1H), 1.33 (s, 3H), 1.47 (m, 1H), 1.57 (m, 1H), 1.69 (m, 1H), 1.99 (m, 1H), 2.18 (s, 3H), 2.07-2.29 (m, 6H), 2.36 (d, 1H), 2.50 (m, 3H), 2.79 (m, 1H), 4.48 (d, 1H, J=17 Hz), 4.73 (d, 1H, J=17 Hz), 5.50 (s, 1H), 5.75 (s, 1H).

Workup

  1. customThe reaction was evaporated in vacuo
  2. customchromatographed on fine silica gel (600 g) in 10-15% ethyl acetate in methylene chloride
  3. customOne fraction of 700 mL was collected

Sources & evidence

ORD record
ord-cbb865437e5e40f5a01d4330fcf403dc
Source dataset
uspto-grants-2015_12
Patent number
US09198921B2

Linked notes

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