Imidazole → HCID 86622724, compound

HRID 1673245Notes

Reaction equation

HRID 1673245 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[C:10]3[C@@H:25](O)[CH2:24][C:23]([CH3:28])([CH3:27])[O:22][C:11]3=[N:12][C:13]=2[C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][C:15]=2[Cl:21])=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[NH:48]1C=CN=C1.[N:53](C(OC(C)C)=O)=[N:54]C(OC(C)C)=O>C(Cl)Cl>[N:48]([C@H:25]1[C:10]2[C:11](=[N:12][C:13]([C:14]3[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][C:15]=3[Cl:21])=[C:8]([C:5]3[CH:4]=[CH:3][C:2]([Cl:1])=[CH:7][CH:6]=3)[CH:9]=2)[O:22][C:23]([CH3:28])([CH3:27])[CH2:24]1)=[N+:53]=[N-:54]

Participants

6

Reactant 4

HCID 795ImidazoleHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 67020012HCID 67020012, compound

Product 1

HCID 86622724HCID 86622724, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a mixture of the product of Example 325, Step A (9.8 g, 22.5 mmol), Zn(N3)2/bis-pyridine complex (Synthesis 1990, 130) (13.9 g, 45.1 mmol), triphenylphosphine (11.8 g, 45.1 mmol), and imidazole (6.1 g, 90 mmol) in 100 mL of CH2Cl2 was added diisopropyl azodicarboxylate (8.8 mL, 45.1 mmol) dropwise at rt. The mixture was allowed to stir at rt for 16 h. The supernatant was separated and washed with diluted HCl (1.0 N, 3×50 mL), saturated aq NaHCO3 (3×50 mL) and brine (50 mL). The organic layer was separated, dried over MgSO4, and concentrated. Chromatography on Biotage 40+M cartridges using 3:17 v/v EtOAc/hexanes as the eluant afforded the product: 1H NMR δ 1.47 (s, 3H), 1.59 (s, 3H), 2.11 (dd, J=9.6, 13.5, 1H), 2.32 (dd, J=6.1, 13.6, 1H), 4.75 (dd, J=6.0, 9.6, 1H), 7.04 (d, J=8.5, 2H), 7.19-7.28 (m, 5H), 7.78 (s, 1H).

Workup

  1. customThe supernatant was separated
  2. washwashed with diluted HCl (1.0 N, 3×50 mL), saturated aq NaHCO3 (3×50 mL) and brine (50 mL)
  3. customThe organic layer was separated
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customafforded the product

Sources & evidence

ORD record
ord-5657e9b406f74e058941c1b93dbaa35c
Source dataset
uspto-grants-2011_08
Patent number
US07999107B2

Reaction notes

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