Oxalyl chloride → HCID 86584828, compound

HRID 1006776Notes

Reaction equation

HRID 1006776 reaction equation
[CH3:1][S:2]([N:5]1[CH2:9][C@H:8]([S:10][C:11]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH2:7][C@H:6]1[C:30](O)=[O:31])(=[O:4])=[O:3].C(Cl)(=O)C(Cl)=O.C[Si]([CH:43]=[N+:44]=[N-:45])(C)C>C(Cl)Cl.CN(C=O)C.CCCCCC>[N+:44](=[CH:43][C:30]([C@@H:6]1[CH2:7][C@@H:8]([S:10][C:11]([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH2:9][N:5]1[S:2]([CH3:1])(=[O:3])=[O:4])=[O:31])=[N-:45]

Participants

7

Reactant 3

HCID 65578Oxalyl chlorideHCID 167693TrimethylsilyldiazomethaneHCID 69431236HCID 69431236, compound

Product 1

HCID 86584828HCID 86584828, compoundYield 48%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolventHCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 25 g (93 mmol) (2S,4R)-1-methanesulfonyl-4-tritylsulfanyl-pyrrolidine-2-carboxylic acid in 265 ml CH2Cl2 at 0° C. was treated with 2 drops of DMF followed by 8 ml (99 mmol) oxalylchloride. After 15 min at 0° C. the reaction was stirred 2 h at room temperature, evaporated and dissolved in 260 ml THF/CH3CN 1:1. 58.5 ml (117 mmol) 2M trimethylsilyldiazomethane solution in hexane was then added at 0° C. The reaction was stirred 16 h at room temperature, evaporated and poured in H2O/EtOAc. The organic phase was dried over Na2SO4, evaporated and purified by flash column chromatography on silica gel with hexane/EtOAc (7:3 to 1:1) to give 12.4 g (48%) of (2S,4R)-2-diazo-1-(1-methanesulfonyl-4-tritylsulfanyl-pyrrolidin-2-yl)-ethanone, MS: 509 (M+NH4+).

Workup

  1. customevaporated
  2. dissolutiondissolved in 260 ml THF/CH3CN 1:1
  3. stirringThe reaction was stirred 16 h at room temperature
  4. customevaporated
  5. additionpoured in H2O/EtOAc
  6. dry with materialThe organic phase was dried over Na2SO4
  7. customevaporated
  8. custompurified by flash column chromatography on silica gel with hexane/EtOAc (7:3 to 1:1)

Sources & evidence

ORD record
ord-ba4967d1afd24c8f9f446d85c542d30d
Source dataset
uspto-grants-2004_09
Patent number
US06790860B2

Reaction notes

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