m-Chloroperbenzoic acid → HCID 71293128, compound

HRID 1404212Notes

Reaction equation

HRID 1404212 reaction equation
[OH:1][CH2:2][CH2:3][NH:4][C:5]([C:7]1[S:11][C:10]([O:12][C:13]2[CH:14]=[C:15]3[C:20](=[CH:21][CH:22]=2)[O:19][C@H:18]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=2[CH3:29])[CH2:17][CH2:16]3)=[N:9][CH:8]=1)=[O:6].N1C=NN=N1.[CH2:35]([O:42][P:43](N(C(C)C)C(C)C)[O:44][CH2:45][C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1)[C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1.ClC1C=CC=C(C(OO)=[O:67])C=1>ClCCl.C(#N)C>[C:24]1([CH3:29])[CH:25]=[CH:26][CH:27]=[CH:28][C:23]=1[C@@H:18]1[CH2:17][CH2:16][C:15]2[C:20](=[CH:21][CH:22]=[C:13]([O:12][C:10]3[S:11][C:7]([C:5]([NH:4][CH2:3][CH2:2][O:1][P:43](=[O:67])([O:42][CH2:35][C:36]4[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=4)[O:44][CH2:45][C:46]4[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=4)=[O:6])=[CH:8][N:9]=3)[CH:14]=2)[O:19]1

Participants

7

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 196621Bis(benzyloxy)(diisopropylamino)phosphineHCID 71509622HCID 71509622, compoundHCID 178418441HCID 178418441, compound

Product 1

HCID 71293128HCID 71293128, compound

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a suspension of 2-((S)-2-o-tolyl-chroman-6-yloxy)-thiazole-5-carboxylic acid (2-hydroxy-ethyl)-amide (1 g, 2.44 mmol) and tetrazole (222 mg, 3.17 mmol, 1.3 eq) in dichloromethane (14 ml) and acetonitrile (14 ml) at 0° C., dibenzyl-N,N-diisopropylphosphoramidite (1.01 g, 2.92 mmol, 1.2 eq) was added and the mixture stirred at 0° C. for 70 min. To the resulting solution 3-chloro-perbenzoic acid (65%, 776 mg, 2.92 mmol, 1.2 eq) was added in one portion and vigorous stirring at 0° C. was continued for 10 min. The mixture was diluted with dichloromethane and the organic layer washed with a saturated aqueous solution of sodium hydrogencarbonate and subsequently with a saturated aqueous solution of ammonium chloride. The combined organic layers were dried over sodium sulfate and filtered, and the solvent removed under reduced pressure. The crude product was purified by column chromatography (silica gel, ethyl acetate). Phosphoric acid dibenzyl ester 2-{[2-((S)-2-o-tolyl-chroman-6-yloxy)-thiazole-5-carbonyl]-amino}-ethyl ester was obtained as a colorless oil (1.30 g, 80%).

Workup

  1. stirringvigorous stirring at 0° C.
  2. waitwas continued for 10 min
  3. washthe organic layer washed with a saturated aqueous solution of sodium hydrogencarbonate and subsequently with a saturated aqueous solution of ammonium chloride
  4. dry with materialThe combined organic layers were dried over sodium sulfate
  5. filtrationfiltered
  6. customthe solvent removed under reduced pressure
  7. customThe crude product was purified by column chromatography (silica gel, ethyl acetate)

Sources & evidence

ORD record
ord-f9bbcc80f39945bb819b082ceb865625
Source dataset
uspto-grants-2014_12
Patent number
US08912224B2

Reaction notes

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