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Dichloromethane → Tert-butyl 3-(6-chloropyridin-3-yl)azetidine-1-carboxylate

HRID 626758
Notes
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Reaction equation

HRID 626758 reaction equation
Cl[Si](C)(C)C.BrCCBr.[C:10]([O:14][C:15]([N:17]1[CH2:20][CH:19](I)[CH2:18]1)=[O:16])([CH3:13])([CH3:12])[CH3:11].C(Cl)Cl.[Cl:25][C:26]1[CH:31]=[C:30](I)[CH:29]=[CH:28][N:27]=1.IC1C=CC=CN=1>CC(N(C)C)=O.[Zn].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].[Cu](I)I>[C:10]([O:14][C:15]([N:17]1[CH2:20][CH:19]([C:29]2[CH:28]=[N:27][C:26]([Cl:25])=[CH:31][CH:30]=2)[CH2:18]1)=[O:16])([CH3:13])([CH3:12])[CH3:11]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

11

Reactant 6

HCID 6344DichloromethaneHCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 2211262-IodopyridineHCID 15165112-Chloro-4-iodopyridineHCID 11000522Tert-butyl 3-iodoazetidine-1-carboxylate

Product 1

HCID 57537370
Tert-butyl 3-(6-chloropyridin-3-yl)azetidine-1-carboxylate
Yield 56%

Reagents, catalysts & solvents 4

HCID 23994ZincCatalyst2×HCID 83717Copper iodideCatalystHCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 31374DimethylacetamideSolvent3×

Procedure

To a de-gassed suspension of zinc powder (912 mg, 14 mmol) in DMA (2.3 mL) was added drop-wise a solution of chlorotrimethylsilane and 1,2-dibromoethane (0.1 mL, 7:5 v/v ratio) and the resultant mixture was stirred at room temperature for 15 minutes. To this mixture was then added dropwise to a solution of 3-iodoazetidine-1-carboxylic acid tert-butyl ester (3.2 g, 11.3 mmol) in DMA (8.0 mL) and the resultant mixture was stirred at room temperature for 15 minutes. In a separate flask, PdCl2(dppf)2.DCM (196 mg, 0.24 mmol) and then copper iodide (92 mg, 0.48 mmol) were added to a degassed solution of 2-chloro-4-iodopyridine in DMA (20 mL). After allowing to age for 30 minutes, the zinc suspension above was added to the iodopyridine solution and the reaction mixture was allowed to stir at room temperature for 2 hours. The resultant mixture was quenched by adding saturated ammonium chloride solution and was then extracted with TBME (×2). The combined organic washings were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel flash chromatography (0-25% ethyl acetate in cyclohexane) to afford the title compound as a white solid (1.2 g, 56%). LCMS (Method F): RT=3.71 min, m/z: 414 [M+H+].

Workup

  1. customThe resultant mixture was quenched
  2. additionby adding saturated ammonium chloride solution
  3. extractionwas then extracted with TBME (×2)
  4. dry with materialThe combined organic washings were dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel flash chromatography (0-25% ethyl acetate in cyclohexane)

Sources & evidence

ORD record
ord-e8e669af4a7948d993ebaee73706818d
Source dataset
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09309240B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes