Dimethyl Sulfoxide → HCID 10257003, compound

HRID 1457474Notes

Reaction equation

HRID 1457474 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[CH2:11]([O:18][C@@H:19]1[CH2:41][C@@H:40]2[C@:35]([CH3:49])([CH2:36][CH2:37][C@H:38]([O:42][CH:43]3[CH2:48][CH2:47][CH2:46][CH2:45][O:44]3)[CH2:39]2)[C@@H:34]2[C@@H:20]1[C@H:21]1[C@:31]([CH3:50])([CH2:32][CH2:33]2)[C@@H:24]([C@H:25]([CH3:30])[CH2:26][CH2:27][CH2:28][OH:29])[CH2:23][CH2:22]1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(N(C(C)C)CC)(C)C.C([O-])(O)=O.[Na+]>C(Cl)Cl>[CH2:11]([O:18][C@@H:19]1[CH2:41][C@@H:40]2[C@:35]([CH3:49])([CH2:36][CH2:37][C@H:38]([O:42][CH:43]3[CH2:48][CH2:47][CH2:46][CH2:45][O:44]3)[CH2:39]2)[C@@H:34]2[C@@H:20]1[C@H:21]1[C@:31]([CH3:50])([CH2:32][CH2:33]2)[C@@H:24]([C@H:25]([CH3:30])[CH2:26][CH2:27][CH:28]=[O:29])[CH2:23][CH2:22]1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

7

Reactant 5

HCID 679Dimethyl SulfoxideHCID 65578Oxalyl chlorideHCID 81531DiisopropylethylamineHCID 516892Sodium BicarbonateHCID 10053347HCID 10053347, compound

Product 1

HCID 10257003HCID 10257003, compoundYield 97%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-78 °C

Procedure

DMSO (0.01 ml, 0.14 mmol) in CH2Cl2 (0.1 ml) was added dropwise to a stirred solution of oxalyl chloride (0.008 ml, 0.0917 mmol) in anhydrous CH2Cl2 (2 ml) at -78° C. under anhydrous conditions (drying tube). This solution was stirred at -78° C. for 15 minutes. Steroid 2008 (0.0234 g, 0.0423 mmol) in dry CH2Cl2 (0.5 ml) was then added dropwise and the solution stirred for 40 minutes at -78° C. Diisopropylethylamine (DIPEA) (0.08 ml, 0.458 mmol) was added and the solution allowed to warm to 0° C. with stirring over a 30-minute period. Aqueous saturated NaHCO3 solution (5 ml) was added and the solution extracted 3× with 5 ml CH2Cl2. The combined organic extracts were washed 2× with 5 ml of aqueous saturated NaCl solution, dried over anhydrous MgSO4, filtered, and the solvent removed in vacuo. Flash chromatography (SiO2, 10:1 hexanes:EtOAc) gave compound 2009 (0.0226 g, 97%) as a white solid foam. 1H NMR (500 MHz, CDCl3) δ: 9.76 (s, 1H, C-24 H), 7.35-7.34 (m, 5H, benzyl Ar-H), 4.71-4.69 (m, 1H, THP ether methine H), 4.59 (d, J=11.8 Hz, 1/2H, benzyl-CH2), 4.585 (d, J=11.8 Hz, 1/2H, benzyl-CH2), 4.30 (d, J=12.0 Hz, 1/2H, benzyl-CH2), 4.29 (d, J=12.0 Hz, 1/2H, benzyl-CH2), 3.95-3.89 (m, 1H, THP OCH2), 3.63-3.58 (m, 3H, C-24 H & THP OCH2), 3.50-3.47 (m, 1H, C-3 H), 3.45 (s, 1H, 7-H), 2.49-2.42 (m, 1H, C-23H), 2.37-2.31 (m, 1H, C-23 H), 0.958 (d, J=6.5 Hz, 3H, C-21 H), 0.81 (s, 3H, C-19 H), 0.63 (s, 3H, C-18 H) (Note: product is a mixture of diastereomers); IR (CHCl3) 2900, 1700 cm-1 ; MS (CI/isobutane) m/z 552 (M+1, 0.4%), 465 (M+1-THP, 3%), 449 (M+1-THPO, 14%), 375 (M+1-THP-Bn, 7%), 359 (M+1-THP-HOBn, 68%), 341 (M+1-THP-HOBn-H2O, 100%); m.p. 50°-54° C.; Anal. calcd. for C36H54O4 : C=78.50, H=9.88; Found: C=78.11, H=10.04.

Workup

  1. stirringthe solution stirred for 40 minutes at -78° C
  2. temperatureto warm to 0° C.
  3. stirringwith stirring over a 30-minute period
  4. extractionthe solution extracted 3× with 5 ml CH2Cl2
  5. washThe combined organic extracts were washed 2× with 5 ml of aqueous saturated NaCl solution
  6. dry with materialdried over anhydrous MgSO4
  7. filtrationfiltered
  8. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-102db6e4d360450897730089f168d524
Source dataset
uspto-grants-1998_12
Patent number
US05847172

Reaction notes

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