Propyl mercaptan → HCID 53240650, compound

HRID 422162Notes

Reaction equation

HRID 422162 reaction equation
[H-].[Li+].[CH2:3](S)CC.C[O:8][C:9]1[CH:26]=[C:25]2[C:12]([C@H:13]3[C@H:22]([CH2:23][S:24]2(=[O:28])=[O:27])[C@:21]2([CH3:29])[C@H:16]([C:17]([CH3:31])([CH3:30])[CH2:18][CH2:19][CH2:20]2)[CH2:15][CH2:14]3)=[C:11]([C:32]([O-:34])=[O:33])[CH:10]=1>CN(P(N(C)C)(N(C)C)=O)C>[OH:8][C:9]1[CH:26]=[C:25]2[C:12]([C@@:13]3([CH3:3])[C@H:22]([CH2:23][S:24]2(=[O:28])=[O:27])[C@:21]2([CH3:29])[C@H:16]([C:17]([CH3:30])([CH3:31])[CH2:18][CH2:19][CH2:20]2)[CH2:15][CH2:14]3)=[C:11]([C:32]([OH:34])=[O:33])[CH:10]=1

Participants

5

Reactant 3

HCID 7848Propyl mercaptanHCID 62714Lithium hydrideHCID 86654193HCID 86654193, compound

Product 1

HCID 53240650HCID 53240650, compoundYield 93.9%

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent2×

Procedure

A mixture of lithium hydride (0.88 g, 110 mmol), 1-propanethiol (11.7 mL, 133 mmol) in HMPA (20 mL) was prepared under N2. The mixture was stirred at room temperature for 30 min. To the mixture, (1R,10S,11S,16S)-5-methoxy-11,15,15-trimethyl-8,8-dioxo-8λ6-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3-carboxylate (64) (4.8 g, 11 mmol) in HMPA (10 mL) was added. The mixture was heated at 130° C. for 1 h. The mixture was cooled to room temperature and quenched with 1 M HCl, then extracted with EtOAc. The organic layer was concentrated to dryness. The crude product was purified by flash chromatography on silica gel (CH2Cl2/MeOH, 10:1) to yield (1R,10R,11S,16S)-5-hydroxy-1,11,15,15-tetramethyl-8,8-dioxo-8λ6-thiatetracyclo[8.8.0.02,7.011,16]-octadeca-2,4,6-triene-3-carboxylic acid (65) (4.2 g, 93%) as a white solid. 1H NMR (CD3OD): δ 7.18 (s, 1H), 6.88 (s, 1H), 3.45 (m, 1H), 2.83 (m, 1H), 2.10 (d, 1H), 1.82-1.35 (m, 10H), 1.20 (m, 2H) 1.00 (m, 5H), 0.89 (s, 3H), 0.85 (s, 3H). MS m/z 405 (C22H30NO5S−H+).

Workup

  1. customwas prepared under N2
  2. temperatureThe mixture was heated at 130° C. for 1 h
  3. temperatureThe mixture was cooled to room temperature
  4. customquenched with 1 M HCl
  5. extractionextracted with EtOAc
  6. concentrationThe organic layer was concentrated to dryness
  7. customThe crude product was purified by flash chromatography on silica gel (CH2Cl2/MeOH, 10:1)

Sources & evidence

ORD record
ord-4057d965975149a0a53b6812a7726713
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

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