Diisopropylethylamine → (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-isocyanato-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one

HRID 1400998Notes

Reaction equation

HRID 1400998 reaction equation
[CH3:1][C@:2]12[C@@:19]3([CH3:20])[C@@H:10]([C@:11]4([CH3:24])[C@@H:16]([CH2:17][CH2:18]3)[C:15]([CH3:22])([CH3:21])[C:14](=[O:23])[CH2:13][CH2:12]4)[CH2:9][CH2:8][C@@H:7]1[C@H:6]1[C@H:25]([C:28]([CH3:30])=[CH2:29])[CH2:26]C[C@]1(C(O)=O)C[CH2:3]2.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:41])C=CC=CC=1.C([N:54]([CH2:58]C)[CH:55]([CH3:57])[CH3:56])(C)C>O1CCOCC1>[N:54]([C@:55]12[CH2:56][CH2:26][C@@H:25]([C:28]([CH3:30])=[CH2:29])[C@@H:6]1[C@@H:7]1[C@@:2]([CH3:1])([CH2:3][CH2:57]2)[C@@:19]2([CH3:20])[C@@H:10]([C@:11]3([CH3:24])[C@@H:16]([CH2:17][CH2:18]2)[C:15]([CH3:21])([CH3:22])[C:14](=[O:23])[CH2:13][CH2:12]3)[CH2:9][CH2:8]1)=[C:58]=[O:41]

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 122844(+)-Betulonic acidHCID 199401P,P-Diphenylphosphinic azide

Product 1

HCID 25426274(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-isocyanato-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-oneYield 92%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (2.1 g, 4.62 mmol) in dioxane (20 mL) was added diphenylphosphoryl azide (DPPA 1.294 mL, 6.00 mmol) and N,N-diisopropylethylamine (2.092 mL, 12.01 mmol) forming a clear solution. The mixture was stirred at RT for 40 minutes before it was immersed into an oil bath at 102° C. under a nitrogen atmosphere for 16 hrs. The crude mixture was evaporated to dryness, re-dissolved into 100 mL DCM, washed 3 times with water. The product was purified by silica gel chromatography eluted with mixture of 20% ethyl acetate in hexanes to give 1.91 gm (92% yield) of the title product. MS: m/e 452.35 (M+H)+, 5.58 min (method 10). 1H NMR (400 MHz, CHLOROFORM-d) δ 4.76 (d, J=2.0 Hz, 1H), 4.66-4.64 (m, 1H), 2.60-2.47 (m, 2H), 2.43 (dd, J=7.5, 4.5 Hz, 1H), 2.11 (br. s., 1H), 1.96-1.77 (m, 5H), 1.76-1.70 (m, 1H), 1.69 (d, J=0.5 Hz, 3H), 1.64-1.42 (m, 10H), 1.42-1.29 (m, 4H), 1.23-1.15 (m, 1H), 1.10 (s, 3H), 1.09 (s, 3H), 1.04 (s, 3H), 0.96 (s, 6H).

Workup

  1. customforming a clear solution
  2. waitwas immersed into an oil bath at 102° C. under a nitrogen atmosphere for 16 hrs
  3. customThe crude mixture was evaporated to dryness
  4. dissolutionre-dissolved into 100 mL DCM
  5. washwashed 3 times with water
  6. customThe product was purified by silica gel chromatography
  7. washeluted with mixture of 20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-7e29ea5c568c4278888e63f247d2a186
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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