1-Butanol → Dendrogenin B

HRID 64382Notes

Reaction equation

HRID 64382 reaction equation
[O:1]1[C@H:3]2[CH:4]=[C:5]3[C@@H:21]([C@@:22]4([CH3:28])[CH2:23][CH2:24][C@H:25]([OH:27])[CH2:26][C:2]124)[CH2:20][CH2:19][C@@:18]1([CH3:29])[C@H:6]3[CH2:7][CH2:8][C@@H:9]1[C@H:10]([CH3:17])[CH2:11][CH2:12][CH2:13][CH:14]([CH3:16])[CH3:15].[NH2:30][CH2:31][CH2:32][CH2:33][CH2:34][NH:35][CH2:36][CH2:37][CH2:38][NH2:39].C(O)CCC>COC(C)(C)C>[CH3:17][C@@H:10]([C@@H:9]1[C@@:18]2([CH3:29])[CH2:19][CH2:20][C@@H:21]3[C@@:22]4([CH3:28])[CH2:23][CH2:24][C@H:25]([OH:27])[CH2:26][C@:2]4([OH:1])[C@H:3]([NH:39][CH2:38][CH2:37][CH2:36][NH:35][CH2:34][CH2:33][CH2:32][CH2:31][NH2:30])[CH:4]=[C:5]3[C@@H:6]2[CH2:7][CH2:8]1)[CH2:11][CH2:12][CH2:13][CH:14]([CH3:15])[CH3:16]

Participants

5

Reactant 3

HCID 2631-ButanolHCID 1102SpermidineHCID 872266475,6alpha-Epoxicholest-7-en-3beta-ol

Product 1

HCID 44598470Dendrogenin BYield 58%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Procedure

5,6α-epoxicholest-7-en-3β-ol (8.9 g, 22.1 mmol, 1 eq) and spermidine (6.4 g, 44.1 mmol, 2 eq) were charged in a round-bottomed flask equipped with a magnetic stirrer bar. 1-Butanol (70 ml, 5 vol) was added and the mixture heated to reflux for 40 h. The reaction mixture was cooled at r.t., diluted with methyl-tertbutyl-ether (5 vol) and washed with water (5 vol) and with brine (5 vol). The organic layer was passed through a silica pad (40 g) eluted with methyl-tertbutyl-ether (3 vol) then 10% Methanol/ethyl acetate (60 vol). Fractions of interest were pooled and the solvent was removed under reduced pressure to give Dendrogenin B (5α-Hydroxy-6β-[4-(3-aminopropylamino)-butylamino]-cholest-7-en-3β-ol) as a white solid (7.0 g, 58%). In same conditions, use of ethanol as solvent (40 vol) and Ca(OTf)2 as catalyst gave a 14% yield.

Workup

  1. customequipped with a magnetic stirrer bar
  2. temperaturethe mixture heated
  3. temperatureto reflux for 40 h
  4. washwashed with water (5 vol) and with brine (5 vol)
  5. washeluted with methyl-tertbutyl-ether (3 vol)
  6. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-866b7642216a4495bf3653c17ae7a0d8
Source dataset
uspto-grants-2016_09
Patent number
US09447141B2

Reaction notes

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