Methanesulfonic Acid → HCID 86585072, compound

HRID 1264420Notes

Reaction equation

HRID 1264420 reaction equation
[CH3:1][S:2]([OH:5])(=[O:4])=[O:3].C(N(CC)CC)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C[O:33][C:34]([C@H:36]1[CH2:40][C@@H:39](O)[CH2:38][N:37]1[C:42]([O:44][C:45]([CH3:48])([CH3:47])[CH3:46])=[O:43])=[O:35].N(C(OC(C)C)=O)=NC(OC(C)C)=O>C1(C)C=CC=CC=1.O>[C:45]([O:44][C:42]([N:37]1[CH2:38][C@@H:39]([O:3][S:2]([CH3:1])(=[O:5])=[O:4])[CH2:40][C@@H:36]1[C:34]([OH:35])=[O:33])=[O:43])([CH3:48])([CH3:46])[CH3:47]

Participants

8

Reactant 5

HCID 6395Methanesulfonic AcidHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 6951202(2R,4R)-4-Hydroxy-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-methyl ester

Product 1

HCID 86585072HCID 86585072, compoundYield 104.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
80 °C

Procedure

To a suspension of 6.7 ml (103.3 mmol) methanesulfonic acid, 14.4 ml (103.3 mmol) triethylamine and 28.8 g (107.6 mmol) triphenylphosphine in 280 ml toluene was added a suspension of 21.12 g (86.12 mmol) (2R,4R)-4-Hydroxy-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-methyl ester [prepared according to “Synthesis of macrocyclic dilactones by cyclization of sulfonium salts”. T. Nakamura, H. Matsuyama, N. Kamigata, M. Iyoda, J. Org. Chem. (1992), 57(14), 3783-9] in 180 ml toluene. After adding 21.6 ml (112 mmol) of diisopropyl azodicaboxylate (exothermic!) the solution was heated for 2.5 h at 80° C. and was stirred at RT for 1 day. 300 ml water was added at RT and extracted with ethylacetate (3×300 ml). The organic phase was washed with aqueous 1M KHSO4 (2×100 ml), brine (2×150 ml), dried over Na2SO4 and evaporated to give 27.85 g (2R,4S)-4-Methanesulfonyloxy-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester as crude product which was dissolved in THF and treated with LiOH according to 5.2.to give (2R,4S)-4-Methanesulfonyloxy-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester.

Workup

  1. additionwas added
  2. extractionextracted with ethylacetate (3×300 ml)
  3. washThe organic phase was washed with aqueous 1M KHSO4 (2×100 ml), brine (2×150 ml)
  4. dry with materialdried over Na2SO4
  5. customevaporated

Sources & evidence

ORD record
ord-d3d5ecfb373e485292df5e7fee820999
Source dataset
uspto-grants-2003_04
Patent number
US06541638B2

Reaction notes

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