Methanesulfonic Acid → (3S,5S)-methanesulfonic acid 5-benzyloxymethyl-1-(naphthalene-2-sulfonyl)-pyrrolidin-3-yl ester

HRID 458374Notes

Reaction equation

HRID 458374 reaction equation
[CH3:1][S:2]([OH:5])(=[O:4])=[O:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:25]([O:32][CH2:33][C@H:34]1[N:38]([S:39]([C:42]2[CH:51]=[CH:50][C:49]3[C:44](=[CH:45][CH:46]=[CH:47][CH:48]=3)[CH:43]=2)(=[O:41])=[O:40])[CH2:37][C@H:36](O)[CH2:35]1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.N(C([O-])=O)=NC([O-])=O>C1(C)C=CC=CC=1.C(N(CC)CC)C>[CH2:25]([O:32][CH2:33][C@H:34]1[N:38]([S:39]([C:42]2[CH:51]=[CH:50][C:49]3[C:44](=[CH:45][CH:46]=[CH:47][CH:48]=3)[CH:43]=2)(=[O:41])=[O:40])[CH2:37][C@@H:36]([O:3][S:2]([CH3:1])(=[O:5])=[O:4])[CH2:35]1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

7

Reactant 4

HCID 6395Methanesulfonic AcidHCID 11776TriphenylphosphineHCID 51573101N-carboxylatoiminocarbamateHCID 69432400(3R,5S)-5-benzyloxymethyl-1-(naphthalene-2-sulfonyl)-pyrrolidin-3-ol

Product 1

HCID 87832403(3S,5S)-methanesulfonic acid 5-benzyloxymethyl-1-(naphthalene-2-sulfonyl)-pyrrolidin-3-yl esterYield 80.9%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8471TriethylamineSolvent

Procedure

To a suspension of methanesulphonic acid (0.96 g) in toluene (30 ml) was added triethylamine (1.40 ml) and triphenylphosphine (2.72 g) at 0–5° C. The suspension was stirred for 5 minutes, and (3R,5S)-5-benzyloxymethyl-1-(naphthalene-2-sulfonyl)-pyrrolidin-3-ol (3.46 g) dissolved in toluene (20 ml) was added dropwise in 5 minutes, followed by diisipropyl azodicarboxylate (2.0 ml). The reaction mixture was stirred for 3 h at 85° C., poured onto ice/water and extracted with ethy acetate. The organic phase was washed with 10% KHSO4— and NaCl solutions, dried over magnesium sulphate and concentrated. The residue was chromatographed on silica gel using EtOAc/hexane 1:2 and 1:1 as eluents to obtain (3S,5S)-methanesulfonic acid 5-benzyloxymethyl-1-(naphthalene-2-sulfonyl)-pyrrolidin-3-yl ester (3.35 g) as a slightly yellow syrup, MS: 476 (MH+).

Workup

  1. additionwas added dropwise in 5 minutes
  2. stirringThe reaction mixture was stirred for 3 h at 85° C.
  3. additionpoured onto ice/water
  4. extractionextracted with ethy acetate
  5. washThe organic phase was washed with 10% KHSO4— and NaCl solutions
  6. dry with materialdried over magnesium sulphate
  7. concentrationconcentrated
  8. customThe residue was chromatographed on silica gel

Sources & evidence

ORD record
ord-9f2f200f7fc145cd9b6d8816dcd9db58
Source dataset
uspto-grants-2007_03
Patent number
US07189756B2

Reaction notes

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