Iodine → HCID 68549795, compound

HRID 470904Notes

Reaction equation

HRID 470904 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.II.[Si:22]([O:29][C@@H:30]([CH3:65])[C@@H:31]([NH:54][C:55]1[CH:60]=[CH:59][C:58]([C:61]#[N:62])=[C:57]([Cl:63])[C:56]=1[CH3:64])[C:32]([NH:34][NH:35][C:36](=[O:53])[C:37]1[CH:42]=[CH:41][C:40]([O:43][CH2:44][C:45]2[CH:50]=[CH:49][C:48]([O:51][CH3:52])=[CH:47][CH:46]=2)=[CH:39][CH:38]=1)=O)([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23]>C(Cl)Cl>[Si:22]([O:29][C@@H:30]([CH3:65])[C@@H:31]([NH:54][C:55]1[CH:60]=[CH:59][C:58]([C:61]#[N:62])=[C:57]([Cl:63])[C:56]=1[CH3:64])[C:32]1[O:53][C:36]([C:37]2[CH:38]=[CH:39][C:40]([O:43][CH2:44][C:45]3[CH:50]=[CH:49][C:48]([O:51][CH3:52])=[CH:47][CH:46]=3)=[CH:41][CH:42]=2)=[N:35][N:34]=1)([C:25]([CH3:26])([CH3:28])[CH3:27])([CH3:24])[CH3:23]

Participants

5

Reactant 3

HCID 807IodineHCID 11776TriphenylphosphineHCID 68545986HCID 68545986, compound

Product 1

HCID 68549795HCID 68549795, compoundYield 87.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Polymer supported Triphenylphosphine (3 g, 8.38 mmol) was dissolved in 250 mL of DCM followed by addition of I2 (2.13 g, 8.38 mmol) and TEA (3.11 mL, 22.36 mmol) at 0° C. N′-((2R,3S)-3-(tert-butyldimethylsilyloxy)-2-(3-chloro-4-cyano-2-methylphenylamino)butanoyl)-4-(4-methoxybenzyloxy)benzohydrazide (3.56 g, 5.59 mmol) in 200 ml DCM was added to the pre-cooled solution mixture of PPh3/I2/TEA system and stirred. The temperature was allowed to warm to room temperature and stirred for additional 10 minutes. The reaction was quenched with 50 ml saturated sodium thiosulfate and the biphasic mixture was separated. The aqueous layer was extracted with EtOAc (3×80 mL) and the combined organic extracts were dried (Na2SO4), filtered and concentrated under reduced pressure. The resulting crude oil was purified by flash chromatography (SiO2) to provide the title compound (3.02 g, 87%). 1H NMR (400 MHz, Acetone d6, δ in ppm): 7.93 (d, J=9 Hz, 2H), 7.48 (d, J=9 Hz, 1H), 7.43 (d, J=9 Hz, 2 H), 7.18 (d, J=9 Hz, 2 H), 6.96 (d, J=9 Hz, 2 H), 6.83 (d, J=9 Hz, 1H) 5.52 (d, J=9 Hz, 1 H), 5.21 (dd, J=2 and 9 Hz, 1 H), 5.13 (s, 2H), 4.73 (m, 1 H), 3.80 (s, 3 H), 2.41 (s, 3H), 1.47 (d, J=6 Hz, 3 H), 0.86 (s, 9 H), 0.11 (s, 3 H), 0.01 (s, 3 H).

Workup

  1. stirringstirred for additional 10 minutes
  2. customThe reaction was quenched with 50 ml saturated sodium thiosulfate
  3. customthe biphasic mixture was separated
  4. extractionThe aqueous layer was extracted with EtOAc (3×80 mL)
  5. dry with materialthe combined organic extracts were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe resulting crude oil was purified by flash chromatography (SiO2)

Sources & evidence

ORD record
ord-7ace39ce4e8e4a40b2a25c5342d9724d
Source dataset
uspto-grants-2014_01
Patent number
US08629167B2

Reaction notes

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