Nitrogen → HCID 131735722, compound

HRID 2201739Notes

Reaction equation

HRID 2201739 reaction equation
N#N.[CH3:3][C:4]([CH3:22])([O:6][C@H:7]1[C@@:15]2([CH3:16])[C@@H:10]([CH2:11][C:12]([OH:21])=[C:13]([C:17]([O:19][CH3:20])=[O:18])[CH2:14]2)[CH2:9][CH2:8]1)[CH3:5].[CH2:23]=[CH:24][C:25](=[O:31])[CH2:26][CH2:27][CH2:28][CH:29]=[CH2:30]>C(Cl)Cl>[CH3:5][C:4]([CH3:22])([O:6][C@H:7]1[C@@:15]2([CH3:16])[C@@H:10]([CH2:11][C:12](=[O:21])[C:13]([CH2:23][CH2:24][C:25](=[O:31])[CH2:26][CH2:27][CH2:28][CH:29]=[CH2:30])([C:17]([O:19][CH3:20])=[O:18])[CH2:14]2)[CH2:9][CH2:8]1)[CH3:3]

Participants

5

Reactant 3

HCID 947NitrogenHCID 118047521,7-octadien-3-oneHCID 131735723HCID 131735723, compound

Product 1

HCID 131735722HCID 131735722, compoundYield 91%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
180 °C

Procedure

Neutral alumina (15 g) was heated in a flask at 180° C. under high vacuum for 4 h. After cooling down to room temperature, the flask was filled with N2. Compound 31 (7.2 g, 25.5 mmol), 1,7-octadien-3-one (4.3 g, 30 mmol), and CH2Cl2 (30 mL) were added to the anhydrous alumina at room temperature. The mixture was stirred at room temperature for 16 h. The suspension was filtered through Celite® 545 which was washed with CH2Cl2 (100 mL×3). The solvent was removed under reduced pressure and the residue was purified by flash column chromatography (silica gel eluted with 10% EtOAc in hexanes) to afford compound 32 (9.4 g, 91%). The compound is a mixture of diastereomers at position C-5 in a 3 to 1 ratio. The major diastereomer had: 1H NMR (CDCl3) δ 5.72-5.60 (m, 1H), 4.95-4.86 (m, 2H), 3.64 (s, 3H), 3.35 (t, J=7.1 Hz, 1H), 1.05 (s, 9H), 0.75 (s, 3H); 13C NMR (CDCl3) δ 209.5, 208.0, 173.7, 137.8, 115.0, 79.9, 72.4, 56.2, 52.2, 46.9, 45.5, 42.4, 42.1, 41.7, 38.1, 32.9, 31.3, 30.5, 28.6, 28.4, 25.5, 22.6; IR νmax 1714, 1641, 1435 cm−1. Anal. Calcd for (C24H38O5): C, 70.90; H, 9.42. Found: C, 71.16; H, 9.70.

Workup

  1. temperatureAfter cooling down to room temperature
  2. filtrationThe suspension was filtered through Celite® 545 which
  3. washwas washed with CH2Cl2 (100 mL×3)
  4. customThe solvent was removed under reduced pressure
  5. customthe residue was purified by flash column chromatography (silica gel eluted with 10% EtOAc in hexanes)

Sources & evidence

ORD record
ord-1d0793dc58c448d3b0be44769a0f3fc1
Source dataset
uspto-grants-2016_06
Patent number
US09365502B2

Reaction notes

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