Acetic Acid → tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((2-(dimethylamino)ethylamino)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate

HRID 405053Notes

Reaction equation

HRID 405053 reaction equation
[CH:1]([C@:3]12[CH2:41][CH2:40][C@@H:39]([C:42]([CH3:44])=[CH2:43])[C@@H:4]1[C@@H:5]1[C@@:18]([CH3:21])([CH2:19][CH2:20]2)[C@@:17]2([CH3:22])[C@@H:8]([C@:9]3([CH3:38])[C@@H:14]([CH2:15][CH2:16]2)[C:13]([CH3:24])([CH3:23])[C:12]([C:25]2[CH:37]=[CH:36][C:28]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])=[CH:27][CH:26]=2)=[CH:11][CH2:10]3)[CH2:7][CH2:6]1)=O.[CH3:45][N:46]([CH3:50])[CH2:47][CH2:48][NH2:49].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].CC(O)=O>ClCCCl>[CH3:45][N:46]([CH3:50])[CH2:47][CH2:48][NH:49][CH2:1][C@:3]12[CH2:41][CH2:40][C@@H:39]([C:42]([CH3:44])=[CH2:43])[C@@H:4]1[C@@H:5]1[C@@:18]([CH3:21])([CH2:19][CH2:20]2)[C@@:17]2([CH3:22])[C@@H:8]([C@:9]3([CH3:38])[C@@H:14]([CH2:15][CH2:16]2)[C:13]([CH3:23])([CH3:24])[C:12]([C:25]2[CH:26]=[CH:27][C:28]([C:29]([O:31][C:32]([CH3:33])([CH3:34])[CH3:35])=[O:30])=[CH:36][CH:37]=2)=[CH:11][CH2:10]3)[CH2:7][CH2:6]1

Participants

6

Reactant 4

HCID 176Acetic Acid2×HCID 66053N,N-DimethylethylenediamineHCID 5049666Sodium triacetoxyborohydride2×HCID 86676397HCID 86676397, compound

Product 1

HCID 86676399tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((2-(dimethylamino)ethylamino)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoateYield 98%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A mixture of tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-formyl-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate (59 mg, 0.099 mmol), N1,N1-dimethylethane-1,2-diamine (0.13 ml, 1.2 mmol), sodium triacetoxyborohydride (104 mg, 0.493 mmol) and AcOH (0.023 ml, 0.394 mmol) in DCE (3 ml) was stirred at rt for 12 h. The solvent was removed in vacuo. LCMS showed desired product and some imine not reduced yet. The residue was redissolved in DCE (3 ml) and treated again with sodium triacetoxyborohydride (104 mg, 0.493 mmol) and AcOH (0.023 ml, 0.394 mmol) at rt for 48 h. Solvent removed in vacuo and the residue redissolved in methylene chloride and purified by silica gel column (0-10% MeOH/CH2Cl2) to afford the title compound as a white solid (65 mg, 98% yield). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.90 (d, J=8.3 Hz, 2H), 7.19 (d, J=8.5 Hz, 2H), 5.30 (dd, J=6.1, 1.6 Hz, 1H), 4.72 (d, J=1.5 Hz, 1H), 4.63 (s, 1H), 3.17-2.95 (m, 3H), 2.72 (t, J=5.9 Hz, 2H), 2.54 (d, J=12.3 Hz, 1H), 2.48-2.41 (m, 1H), 2.40 (s, 6H), 2.21-1.10 (m, 22H), 1.72 (s, 3H), 1.61 (s, 9H), 1.12 (s, 3H), 1.03 (s, 3H), 1.00 (s, 3H), 0.95 (s, 6H).

Workup

  1. customThe solvent was removed in vacuo
  2. dissolutionThe residue was redissolved in DCE (3 ml)
  3. customSolvent removed in vacuo
  4. dissolutionthe residue redissolved in methylene chloride
  5. custompurified by silica gel column (0-10% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-24343943a78045e8995c6151a7bebdb4
Source dataset
uspto-grants-2014_06
Patent number
US08748415B2

Reaction notes

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