Iodine → HCID 136343397, compound

HRID 2388434Notes

Reaction equation

HRID 2388434 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.II.[Si]([O:29][C:30]1[CH:63]=[CH:62][C:33]([C:34]([NH:36][NH:37][C:38](=O)[C@H:39]([NH:50][C:51]2[CH:56]=[CH:55][C:54]([C:57]#[N:58])=[C:53]([Cl:59])[C:52]=2[CH3:60])[C@H:40]([O:42][Si:43]([C:46]([CH3:49])([CH3:48])[CH3:47])([CH3:45])[CH3:44])[CH3:41])=[O:35])=[CH:32][C:31]=1[Cl:64])(C(C)(C)C)(C)C>C(Cl)Cl>[Si:43]([O:42][C@H:40]([CH3:41])[C@@H:39]([NH:50][C:51]1[CH:56]=[CH:55][C:54]([C:57]#[N:58])=[C:53]([Cl:59])[C:52]=1[CH3:60])[C:38]1[O:35][C:34]([C:33]2[CH:62]=[CH:63][C:30]([OH:29])=[C:31]([Cl:64])[CH:32]=2)=[N:36][N:37]=1)([C:46]([CH3:48])([CH3:47])[CH3:49])([CH3:44])[CH3:45]

Participants

5

Reactant 3

HCID 807IodineHCID 11776TriphenylphosphineHCID 67007005HCID 67007005, compound

Product 1

HCID 136343397HCID 136343397, compoundYield 106.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a 25 mL round bottom flask was added polymer supported triphenylphosphine (687 mg, 2.06 mmol, 2.0 equiv., approx. 3 mmol/g) and 10.3 mL of methylene chloride. The reaction was cooled to 0° C. using an ice-water bath and then iodine (523 mg, 2.06 mmol, 2.0 equiv.) was added followed by TEA (0.57 mL, 4.12 mmol, 4.0 equiv.). After stirring for 5 min, 4-(tert-butyldimethylsilyloxy)-N′-((2R,3R)-3-(tert-butyldimethylsilyloxy)-2-(3-chloro-4-cyano-2-methylphenylamino)butanoyl)-3-chloro benzohydrazide (688 mg, 1.03 mmol, 1.0 equiv.) was added. The reaction was allowed to stir at room temperature for 2 h. The mixture was filtered over Celite® in a ground glass fritted funnel and the solids rinsed with methylene chloride several times. The organics were washed with 10% Na2S2O3 (3×10 mL) followed by a wash with brine (1×10 mL). The solution was dried over Na2SO4 and was concentrated in vacuo to yield a brown oil. The product was purified via automated flash chromatography (0→30% EtOAc/hexanes→100% EtOAc, 40 g of silica gel) to provide the desired product as a yellow oil (586 mg, 88% yield). Other data: 1H NMR (400 MHz, acetone-d6, δ in ppm) 7.92 (d, J=2.14 Hz, 1H), 7.80 (dd, J=1.95, 8.4 Hz, 1H), 7.50 (d, J=8.79 Hz, 1H), 7.18 (d, J=8.6 Hz, 1H), 6.93 (d, J=8.79 Hz, 1H), 5.79 (d, J=9.18 Hz, 1H), 5.02 (dd, J=6.65, 9.19 Hz, 1H), 4.65 (m, 1H), 2.34 (s, 3H), 1.41 (d, J=6.05 Hz, 3H), 0.81 (s, 9H), 0.09 (s, 3H), 0.03 (s, 3H); LRMS (ESI-) exact mass calcd for C25H30Cl2N4O3Si [M]+533.5, found 534.2.

Workup

  1. additionTo a 25 mL round bottom flask was added polymer
  2. stirringto stir at room temperature for 2 h
  3. filtrationThe mixture was filtered over Celite® in a ground glass fritted funnel
  4. washthe solids rinsed with methylene chloride several times
  5. washThe organics were washed with 10% Na2S2O3 (3×10 mL)
  6. washa wash with brine (1×10 mL)
  7. dry with materialThe solution was dried over Na2SO4
  8. concentrationwas concentrated in vacuo
  9. customto yield a brown oil
  10. customThe product was purified

Sources & evidence

ORD record
ord-f2c172bec55d4b1db489d5b4fc725a2a
Source dataset
uspto-grants-2012_09
Patent number
US08268872B2

Reaction notes

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