Benzenemethanethiol, alpha,alpha-diphenyl- → (2S,4R)-1-(naphthalene-2-sulfonyl)-4-tritylsulfanyl-pyrrolidine-2-carboxylic acid methyl ester

HRID 1006773Notes

Reaction equation

HRID 1006773 reaction equation
[C:1]1([C:7]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[SH:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.CC([O-])(C)C.[K+].[CH3:27][O:28][C:29]([C@@H:31]1[CH2:35][C@H:34](OS(C)(=O)=O)[CH2:33][N:32]1[S:41]([C:44]1[CH:53]=[CH:52][C:51]2[C:46](=[CH:47][CH:48]=[CH:49][CH:50]=2)[CH:45]=1)(=[O:43])=[O:42])=[O:30]>CN(C=O)C>[CH3:27][O:28][C:29]([C@@H:31]1[CH2:35][C@@H:34]([S:8][C:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)([C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=2)[CH2:33][N:32]1[S:41]([C:44]1[CH:53]=[CH:52][C:51]2[C:46](=[CH:47][CH:48]=[CH:49][CH:50]=2)[CH:45]=1)(=[O:43])=[O:42])=[O:30]

Participants

5

Reactant 3

HCID 77281Benzenemethanethiol, alpha,alpha-diphenyl-HCID 11441344(4S,2S)-4-Methanesulfonyloxy-1-(naphthalene-2-sulfonyl)-pyrrolidine-2-carboxylic acid methylesterHCID 23665647Potassium tert-butoxide

Product 1

HCID 69435513(2S,4R)-1-(naphthalene-2-sulfonyl)-4-tritylsulfanyl-pyrrolidine-2-carboxylic acid methyl ester

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
100 °C

Procedure

64.2 g (167 mmol) of triphenylmethanthiol was slowly added at room temperature to a solution of 17.9 g (160 mmol) of potassium tert-butylate in 300 ml DMF and stirred mechanically for 30 min. Then 63 g (152 mmol) of (4S,2S)-4-methanesulfonyloxy-1-(naphthalene-2-sulfonyl)-pyrrolidine-2-carboxylic acid methylester in 300 ml DMF were added at 20° C. by cooling at the end with an ice bath. The reaction was heated for 1.3 h at 100° C., cooled, evaporated to 400 ml and extracted with 250 ml aqueous saturated NH4Cl/EtOAc (3×300). The organic phases were washed with aq. 10% NaCl, dried (Na2SO4) and evaporated. Flash chromatography (CH2Cl2/MeOH 99:1) gave 58.6 g (65%, (2S,4R)/(2R,4R)-isomer ca 4:1, 1H-NMR) and 9.2 g (10%, (2S,4R)/(2R,4R)-isomer ca 1:1, 1H-NMR) of (2S,4R)-1-(naphthalene-2-sulfonyl)-4-tritylsulfanyl-pyrrolidine-2-carboxylic acid methyl ester, MS: 594 (MH+).

Workup

  1. temperatureby cooling at the end with an ice bath
  2. temperaturecooled
  3. customevaporated to 400 ml
  4. extractionextracted with 250 ml aqueous saturated NH4Cl/EtOAc (3×300)
  5. washThe organic phases were washed with aq. 10% NaCl
  6. dry with materialdried (Na2SO4)
  7. customevaporated

Sources & evidence

ORD record
ord-a03c04aec94d49d9820b630c5b0afe33
Source dataset
uspto-grants-2004_09
Patent number
US06790860B2

Reaction notes

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