Nitrogen → HCID 57250906, compound

HRID 1456007Notes

Reaction equation

HRID 1456007 reaction equation
[OH:1][C@H:2]1[CH2:26][CH2:25][C@@:24]2([CH3:27])[C:4](=[CH:5][C:6](=[O:29])[C@@H:7]3[C@@H:23]2[CH2:22][CH2:21][C@@:20]2([CH3:28])[C@H:8]3[CH2:9][CH2:10][C@@H:11]2[C@H:12]([CH3:19])[CH2:13][CH2:14][C:15]([O:17][CH3:18])=[O:16])[CH2:3]1.N1C(C)=CC=CC=1C.N#N.FC(F)(F)S(O[Si:46]([CH:53]([CH3:55])[CH3:54])([CH:50]([CH3:52])[CH3:51])[CH:47]([CH3:49])[CH3:48])(=O)=O>C(Cl)Cl>[O:29]=[C:6]1[CH:5]=[C:4]2[C@:24]([CH3:27])([CH2:25][CH2:26][C@H:2]([O:1][Si:46]([CH:53]([CH3:55])[CH3:54])([CH:50]([CH3:52])[CH3:51])[CH:47]([CH3:49])[CH3:48])[CH2:3]2)[C@@H:23]2[C@@H:7]1[C@H:8]1[C@:20]([CH3:28])([CH2:21][CH2:22]2)[C@@H:11]([C@H:12]([CH3:19])[CH2:13][CH2:14][C:15]([O:17][CH3:18])=[O:16])[CH2:10][CH2:9]1

Participants

6

Reactant 4

HCID 947NitrogenHCID 79372,6-LutidineHCID 2724529Triisopropylsilyl trifluoromethanesulfonateHCID 23250094Methyl (3β)-3-hydroxy-7-oxochol-5-en-24-oate

Product 1

HCID 57250906HCID 57250906, compoundYield 84.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of methyl 3β-hydroxy-7-oxochol-5-en-24-oate (2) (5.02 g, 12.5 mmoles) and 2,6-lutidine (3.32 ml, 28.5 mmoles) in CH2Cl2 (23 ml) cooled in an ice bath in a N2 atmosphere was added dropwise with magnetic stirring triisopropylsilyl trifluoromethanesulfonate (4.56 g, 17 mmoles). After 2 hrs, the reaction was diluted with CH2Cl2 (150 ml). It was then washed with cold 2N HCI, washed twice with H2O and then with saturated brine before drying with MgSO4. Evaporation in vacuo and purification of the residue by flash chromatography on silica gel with hexane-EtOAc (10:1) gave 5.88 g of 3 as a colorless syrup. NMR (CDCl3): δ 0.67 (s, 3H, 18-Me); 0.93 (d, 3H, 20-Me); 1.06 (s, 18H, TIPS Me); 1.19 (s, 3H, 19-Me); 3.66 (s, 3H, CO2Me); 3.68 (m, 1H, 3-H); 5.66 (s, 1H, 6-H).

Workup

  1. additionwas added dropwise
  2. washIt was then washed with cold 2N HCI
  3. washwashed twice with H2O
  4. dry with materialwith saturated brine before drying with MgSO4
  5. customEvaporation
  6. customin vacuo and purification of the residue by flash chromatography on silica gel with hexane-EtOAc (10:1)

Sources & evidence

ORD record
ord-a51b04f147f54a7ea17556147262193a
Source dataset
uspto-grants-1998_12
Patent number
US05843953

Reaction notes

Loading…