Ethylenediamine → (3R,4S,5R)-5-amino-3-(1-ethyl-propoxy)-4-methanesulfonyloxy-cyclohex-1-enecarboxylic acid ethyl ester

HRID 495687Notes

Reaction equation

HRID 495687 reaction equation
[Na+].[CH2:2]([O:4][C:5]([C:7]1[CH2:8][C@@H:9]([N:20]=CC2C=CC=CC=2S([O-])(=O)=O)[C@H:10]([OH:19])[C@H:11]([O:13][CH:14]([CH2:17][CH3:18])[CH2:15][CH3:16])[CH:12]=1)=[O:6])[CH3:3].C(N(CC)CC)C.[CH3:39][S:40](Cl)(=[O:42])=[O:41].C(N)CN>C(OCC)(=O)C.O>[CH2:2]([O:4][C:5]([C:7]1[CH2:8][C@@H:9]([NH2:20])[C@H:10]([O:19][S:40]([CH3:39])(=[O:42])=[O:41])[C@H:11]([O:13][CH:14]([CH2:15][CH3:16])[CH2:17][CH3:18])[CH:12]=1)=[O:6])[CH3:3]

Participants

7

Reactant 4

HCID 3301EthylenediamineHCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 87986406(1r,5r,6s)-2-{[3-Ethoxycarbonyl-5-(1-ethyl-propoxy)-6-hydroxy-cyclohex-3-enylimino]-methyl}-benzenesulfonic acid sodium salt

Product 1

HCID 10593945(3R,4S,5R)-5-amino-3-(1-ethyl-propoxy)-4-methanesulfonyloxy-cyclohex-1-enecarboxylic acid ethyl esterYield 91%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred suspension of 9.23 g (20 mmol) (1R,5R,6S)-2-{[3-ethoxycarbonyl-5-(1-ethylpropoxy)-6-hydroxy-cyclohex-3-enylimino]-methyl}-benzenesulfonic acid sodium salt and 3.50 ml (25 mmol) of triethylamine in 90 ml ethyl acetate was added 1.80 ml (23 mmol) methanesulfonyl chloride at to 0 to 5° C. The resulting brown-yellowish suspension was stirred at room temperature for 2 hours, treated with 2.70 ml (40 mmol) ethylenediamine and after 10 min with 90 ml of water. After stirring the 2-phase system vigorously for 1 hour the organic phase was separated and extracted with 100 ml water and 3 times with 100 ml aqueous 1M NaHCO3 solution, dried over Na2SO4, filtered and evaporated in a rotary evaporator at 48° C./4 mbar to dryness to yield 6.36 g (91%) of (3R,4S,5R)-5-amino-3-(1-ethyl-propoxy)-4-methanesulfonyloxy-cyclohex-1-enecarboxylic acid ethyl ester as an orange oil. An analytical sample of was obtained by column chromatography on silica gel using t-BuOMe containing 1% of 25% ammonia as the eluent. IR (film): 2966, 2936, 2878, 1711, 1653, 1463, 1351, 1246, 1172, 1068, 961 cm−1; MS (EI, 7o eV)):350 (M+), 262, 224, 182, 166, 136 m/z.

Workup

  1. stirringAfter stirring the 2-phase system vigorously for 1 hour the organic phase
  2. customwas separated
  3. extractionextracted with 100 ml water and 3 times with 100 ml aqueous 1M NaHCO3 solution
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. customevaporated in a rotary evaporator at 48° C./4 mbar to dryness

Sources & evidence

ORD record
ord-1195026657ad4ae4a41e2b931e28b937
Source dataset
uspto-grants-2005_09
Patent number
US06939986B2

Reaction notes

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