Lithium Hexamethyldisilazide → 2-(3,5-Dichloropyridin-4-yl)-1-{9-methoxy-spiro[2H-1,5-benzodioxepin-3(4H),5'-[1,3]dioxane]-6-yl}ethanone

HRID 2196113Notes

Reaction equation

HRID 2196113 reaction equation
[Cl:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Cl:9])[C:7]=1[CH3:8].C[O:11][C:12]([C:14]1[C:29]2[O:28][CH2:27][C:21]3([CH2:26][O:25][CH2:24][O:23][CH2:22]3)[CH2:20][O:19][C:18]=2[C:17]([O:30][CH3:31])=[CH:16][CH:15]=1)=O.[Li+].C[Si]([N-][Si](C)(C)C)(C)C>C1COCC1>[Cl:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Cl:9])[C:7]=1[CH2:8][C:12]([C:14]1[C:29]2[O:28][CH2:27][C:21]3([CH2:26][O:25][CH2:24][O:23][CH2:22]3)[CH2:20][O:19][C:18]=2[C:17]([O:30][CH3:31])=[CH:16][CH:15]=1)=[O:11]

Participants

5

Reactant 3

HCID 2733832Lithium HexamethyldisilazideHCID 109538273,5-Dichloro-4-methylpyridineHCID 592867099-Methoxy-spiro[2H-1,5-benzodioxepin-3(4H),5'-[1,3]dioxane]-6-carboxylic acid methyl ester

Product 1

HCID 250055272-(3,5-Dichloropyridin-4-yl)-1-{9-methoxy-spiro[2H-1,5-benzodioxepin-3(4H),5'-[1,3]dioxane]-6-yl}ethanone

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Following the general procedure, condensation of 3,5-dichloro-4-methylpyridine (211 mg, 1.3 mmol) with compound 524 (310 mg, 1.0 mmol) in THF (6 mL) in the presence of LiHMDS (3 mL, 3.0 mmol) afforded compound 130 as a white solid material after purification by column chromatography (60-80% EtOAc in light petroleum). LC-MS: RT=3.64 min.; m/z 440.16, 442.17 (M+H)+, 438.27, 440.29 (M−H). 1H NMR (DMSO-d6): δ 8.65 (2H, s), 7.43 (1H, d, J 8.9), 6.89 (1H, d, J 8.9), 4.84 (1H, d, J 6.1), 4.79 (1H, d, J 6.1), 4.64 (2H, s), 4.34 (2H, s), 4.08 (2H, s), 3.90 (2H, d, J 11.4), 3.85 (3H, s), 3.82 (2H, d, J 11.2).

Sources & evidence

ORD record
ord-09656510375342ac933bdbf10e89b20e
Source dataset
uspto-grants-2012_12
Patent number
US08338431B2

Reaction notes

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