Triphenylphosphine → HCID 46188460, compound

HRID 1505296Notes

Reaction equation

HRID 1505296 reaction equation
[CH:1]1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Li]CCCC.[C:25]([N:32]1[C@@H:41]([CH2:42]O)[CH2:40][C:39]2[C:34](=[C:35]3[CH:55]=[CH:54][C:53]([O:56][CH3:57])=[CH:52][C:36]3=[C:37]3[CH:47]=[C:46]([O:48][CH3:49])[C:45]([O:50][CH3:51])=[CH:44][C:38]3=2)[CH2:33]1)([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26].[NH4+].[Cl-]>C1COCC1>[C:28]([O:27][C:25]([N:32]1[C@H:41]([CH:42]=[CH2:1])[CH2:40][C:39]2[C:34](=[C:35]3[CH:55]=[CH:54][C:53]([O:56][CH3:57])=[CH:52][C:36]3=[C:37]3[CH:47]=[C:46]([O:48][CH3:49])[C:45]([O:50][CH3:51])=[CH:44][C:38]3=2)[CH2:33]1)=[O:26])([CH3:30])([CH3:29])[CH3:31]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 25517Ammonium ChlorideHCID 53388821HCID 53388821, compoundHCID 178418339Butyllithium

Product 1

HCID 46188460HCID 46188460, compoundYield 76%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of Ph3P═CH2Br (1.43 g, 4 mmol) in THF was added n-BuLi (2M in heptanes, 1.95 mL) at 0° C. under N2. The mixture was stirred for 0.5 h before compound 8 (906 mg, 2 mmol) in THF (20 mL) was added dropwise. The mixture was then stirred for 2 h (monitored by TLC). Sat. NH4Cl was added to quench the reaction and THF was removed by evaporation. The residue was dissolved in CH2Cl2 (50 mL), washed with sat. NaHCO3 and brine, and dried over MgSO4. Column chromatography eluting with EtOAc/Hexane gave 9 (684 mg, 76%) as a light yellow foam: mp 177-179° C.; [α]23D=118.2 (c 0.56, CHCl3); 1H NMR (300 MHz, CDCl3): δ 7.92 (s, 1H), 7.91 (d, J=2.4 Hz, 1H), 7.85 (d, J=9.0 Hz, 1H), 7.31 (s, 1H), 7.23 (dd, J=9.0 Hz, J=2.7 Hz, 1H), 5.86-5.75 (m, 1H), 5.29 (m, 1H), 5.26 (d, J=16.8 Hz, 1H), 5.16-5.04 (m, 2H), 4.59 (d, J=17.4 Hz, 1H), 4.11 (s, 3H), 4.06 (s, 3H), 4.01 (s, 3H), 3.36 (dd, J=16.2 Hz, J=6.0 Hz, 1H), 3.29 (t, J=16.5 Hz, 1H), 1.55 (s, 9H); 13C NMR (75 MHz, CDCl3): δ 157.9, 155.3, 149.8, 148.8, 136.5, 130.4, 126.8, 124.4, 124.2, 123.9, 123.6, 123.1, 116.6, 115.2, 105.1, 104.3, 104.1, 80.3, 77.4, 56.3, 56.1, 55.7, 41.1, 29.8, 28.7 (3×C); ESI-HRMS ([M+Na]+) calcd for C27H31NO5Na 472.2100. found 472.2103.

Workup

  1. additionwas added dropwise
  2. customto quench
  3. customthe reaction and THF
  4. customwas removed by evaporation
  5. dissolutionThe residue was dissolved in CH2Cl2 (50 mL)
  6. washwashed with sat. NaHCO3 and brine
  7. dry with materialdried over MgSO4
  8. washColumn chromatography eluting with EtOAc/Hexane

Sources & evidence

ORD record
ord-aa7a091d9eca407b8c3ba3d60edbc4e3
Source dataset
uspto-grants-2015_12
Patent number
US09216977B2

Reaction notes

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